Apart from a programming exercise and teaching moment, why would you want to get a random key and value from a dict? In 25-ish years of using Python, I think that the number of times I've needed to do that is zero. A random item from a list, dozens of times. But from a dict, never.
(I'm not even convinced that dict.popitem is useful either. But maybe that's just me, and others use it ten times a day.)