What information to gather
Be as specific in your questions as possible. Ask for confirmation of previous employment history-position title, length of employment, duties performed, projects worked on, responsibilities (budgetary, supervisory, etc), reason for leaving, etc.
A common question is whether the referee would rehire the candidate at the same level, and if not, why not. The answer to this question should tell you a lot about the past performance of the employee--although you need to be careful in case the answer is influenced by personal bias. Some organisations have policies against giving information in references because of possible legal implications.
For example, defamation charges may be brought if it is found that the referee has ‘disseminated false or derogatory statements’ about them. It is much safer just to give basic employment information.
If a referee is unable to say much, do not infer that this is because of poor performance. Look for recurring similar accounts, as one negative report could just indicate a personality clash or a problem with the referee rather than the candidate. It is most useful to use a standardised form for reference checks. This ensures that all relevant questions are asked and that no questions are asked that could breach EEO or discrimination laws.