I'm not aware of any clear-cut answer on this one from the medical literature. However, what's most important, is that you take it at a time that's convenient for you. Like medications, one of the most difficult challenges for people is to remember to take the multivitamin in the first place.
Depending on what exactly you're taking, some vitamins might be best taken with or without food. For example, it is not recommended to take an iron supplement with coffee, tea or milk. That being said, if your multivitamin contains iron, I'd recommend not taking it before your morning latté. For a regular multivitamin without iron, consider taking it along with a healthy breakfast.
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