As a retained executive search firm here in Austin, we have an interview process that heavily relies on active listening. The candidate will tell you everything if you listen and then you can make the best assessment. Get them to do most of the talking.
This is my method for getting candidates to do most of the talking:
1) Have them talk thru each job on their resume. Pay special attention as to why they left each job. This will paint a huge picture on  business maturity.
2) Ask what is their motivation for wanting to be hired by your organization. You will be able to sell the candidate on the opportunity later by understanding what motivates them.
3) Ask them to articulate their operating style in the workplace. This will give you feedback on whether they are a fit for your culture. This is a huge question. Without a culture fit, you do not have a candidate.
4) Have them articulate how they are a strong technical fit for your position. This will give you a sense of how well they prepared for the interview. It will also give you a sense of  technical fit. In the end, however, you have to make the call on whether or not they are a technical fit for the position.
5) If there is a relocation involved, ask them if there is anyone they are close to that will be effected by this decision. When people consider moving to another locale, you must assess if they are truly up for the move.
6) Share the compensation range with the candidate and make sure it matches their expectation level. If it does not, find out what does in a general way (assuming this is the first interview). If they are a great candidate, keep the door open at this point in the conversation as the client may agree with your assessment and consider paying them a higher range if they are a game changing candidate.
7) Find out if they are interviewing with other companies so you can address who your competition is.
8) Share the job description with the candidate and go over warts and all. Make sure they are up to the challenge and have a realistic understanding of the challenges.
Getting the candidate to talk allows you to make the right selection but only if you are LISTENING as an interviewer. Candidates will tell you everything you need to know to strike a win-win deal for client and candidate alike.