FORTUNE — In an age where people “connect” with or “friend” each other without so much as shaking hands and where some coworkers who work on projects together never meet in person, how do you go about finding an ideal mentor?

Web-based programs may make it easier for companies to offer mentoring opportunities to employees, but you still have to do the hard work of building a useful relationship.

Consider Sodexo. Before the food services and facilities management company launched an e-mentoring program several years ago, the company sponsored from 45 to 125 new mentoring partnerships each year, says Jodi Davidson, director of diversity and inclusion initiatives. But Sodexo has a U.S. workforce of 115,000 employees and about 15,000 managers who could benefit from a mentorship program.

The one-on-one nature of the formal program “was not going to allow everyone to take part,” says Davidson. So Sodexo has begun to use software by Greenwood Village, Colo.-based Triple Creek, which uses an algorithm to suggest ideal mentor-mentee matches.

Now, Sodexo has an informal program open to all managers that has about 1,700 mentees and 1,300 mentors and it continues to have about 125 formal mentoring partnerships.

Financial manager Northern Trust also relies on technology to open up the mentoring process to its more than 13,000 employees across the globe. Northern Trust also uses Triple Creek’s mentoring software.

Web-based mentoring doesn’t necessarily save a company money, because it requires an initial investment in the software, says Northern Trust spokesperson Sophia Venetos. “Setting up a traditional face-to-face, manually run program doesn’t require much upfront investment, but [does] require significant time and resources to manage.”

It’s the relationship that counts

Whether online or face-to-face, mentoring is “a social relationship,” says Daniel Debow, co-CEO of Rypple, which produces performance management software. Any technology “should facilitate deeper, richer relationships.”

It all comes down to your commitment to that relationship, says Lois Zachary, director of the Phoenix-based Center for Mentoring Excellence and author of The Mentor’s Guide: Facilitating Effective Learning Relationships. The right mentor “can be in Timbuktu or New York but you have to understand who that individual is and what they bring to the relationship.”

Zachary recommends identifying specific goals you want to achieve and establishing criteria to determine the right mentor to help you reach them.

“Learning is the purpose, the process, and the product of mentoring. It’s why you do it.”

Kathy Bollinger, president of the Arizona West Region of the Banner Health system of hospitals, has plenty of experience as a mentor and as a mentee.

Over the years, Bollinger finds she has become much more selective about giving up her time to mentor others. “I want to make sure I’m the right and best person for what that person wants to accomplish … It’s a contract, a commitment.”

Bollinger has taken on Julie B. Sherman, Banner Health’s senior director of brand services, as a mentor.

To make the most of the partnership, Sherman says, “We reviewed my responsibilities as a mentee, and my expectations and goals. We agreed to a meeting schedule and … that it was my responsibility to guide our conversations to make the most out of my time with her. She asks very powerful questions that really make one think.”

With Bollinger’s support, Sherman says she was able to oversee a major restructuring that eliminated $800,000 in expenses for Banner Health.

Kris McMasters, CEO of public accounting firm Clifton Gunderson, believes that the best mentors “make people think they can do things they don’t even think they have the ability to do. They make them stretch.”

McMasters, who has had a number of mentors over the course of her career, says Clifton Gunderson finds it best to match people up, using traditional methods, with mentors who have had experience in the same area of service, such as taxes, assurance, or accounting. That way, “they understand what it means to come up in that position.”

Before McMasters became CEO, her mentor was her then-CEO boss. “He put the onus on me to be successful. He was not spoon feeding me,” she says.

For example, “I went to him, I said I wasn’t happy with the level of turnover. He said, ‘write a strategy paper on what we should do differently.’ I looked at other professional services organizations and met with him periodically. He made recommendations. At that time, I had no HR background. I learned a ton from it,” McMasters says.

Sticking to a set of ground rules

Lois Zachary urges mentors and mentees to establish ground rules before they begin a relationship. “Put it all out on the table at the beginning. Talk about stumbling blocks. About confidentiality. How do you close the relationship if it doesn’t work out?”

As a mentee, it’s best to establish a process and always have a mentoring date on the calendar, Zachary advises. Ask your mentor for what you need. And ask yourself if you are making progress on your goals. “Make sure you are on track, don’t just wait for things to go off the rails,” she says.

Keeping the relationship on track is where social software can help, says Daniel Debow. “It’s a shared private space for the two of you to keep notes [and] set goals.”

And if you’re handling the relationship professionally, there’s no need to feel bad about taking up your mentor’s time. “We hear in our research and interviews that the mentor gets more out of it than the mentee,” Zachary says. Mentoring “gives them perspective. It reengages them and reconnects them to what they’re doing. They learn about things going on in their company, in their field.”