We have an awesome interactions checker on this site. Other than that I would point you to the prescribing physician on this. I had the same issue and it resulted in my choice of one or the other. For me (we are all different), Valium helps me sleep longer, while Ambien helped me fall asleep faster, but didn't help with the length of sleep.
Also, when I was taking both, I was having weird dreams which made the quality of the overall sleep less.
Hope this feedback helps a bit.
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