Homework first! They can snack while doing it, but we get homework outta the way and then on to the fun. I will say that in the winter when the days are shorter, I'll sometimes let them put off their homework in order to maximize whatever daylight is left.
It really depends. If hubby is home with the kids he will sometimes make sure the homework gets done before I get home. If hubby is at work and kids are in daycare then I make sure it all gets done as soon as dinner is over.