If humans had hooves, it would be so because they evolved to have hooves. In the course of this evolution process, they would have to be able to walk (or run) in order to find food, escape predators and so on, so the answer would have to be yes.
If you're asking "if people miraculously had their feet replaced by hooves, would they be able to walk" the answer would have to be "depends on the exact properties of these hooves". This is not a biological question IMO, it's more about biomechanics, and there's not enough data to answer it.