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Around 20 weeks is when they can determine the sex of the baby. Even then it's not 100%.
I agree with MrsCastaneda.. My drs have told us with both pregnancies that between 19 and 21 weeks is the best time to find out..although its not 100% accurate even then =)
If you have an amniocentises they can tell for sure by the chromosomes. Not everyone needs that test though. If you have it, I think it is around 12-14 weeks.
I strongly advise against getting an amniosentesis. The risks outweigh the benefits greatly. Unless you ABSOLTELY HAVE to have one, which is ordered by a doctor, don't get one.