Besides the topics that eyepopslikeamosquito mentioned, the generic 'what was your most miserable failure?' with a followup of 'what would you have done differently, in hindsight?' can give you some insight into a person's personality.
From the last time I had to hire someone, here are the generic questions that I asked:
- Tell us about yourself (note -- forces them to summarize their resume to what they think is important)
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What is your most proud accomplishment, and why?
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What action do you most regret, and why?
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What is the worst job you've ever had?
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What goals do you have in your career?
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What are your long term goals?
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What motivates you?
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What is your greatest weakness?
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What specific skills and experience do you feel set you
apart from others who might have applied for this job?
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Why do you want to work for (insert organization)?
update: fixed a typo.