Steaming while boiling food

Yes, if you have the right pot, namely one that has a steamer insert that is well above the bottom of the pot, or even stacks.

In fact, in several cuisines this is the standard way of getting several ingredients ready at once. For example, it's common to steam couscous in the steam from the Moroccan stew cooking below, using a stacking pot called a couscousiere.

Just make sure that the food in the steamer will take less time to steam than the food below takes to boil.