Is there a connection between UV-degradation and the photoelectric effect
Yes and no. 

In a metal, the photoelectric effect is when a UV photon has enough energy to push an electron from it's current energy level to at least the $n=\infty$ level. Extra energy goes into electron kinetic energy.

For UV degradation, we are promoting elections to higher energy orbitals in an analogous way. This produces an energized state that is highly reactive and may undergo radical reactions that ultimately lead to the formation of different species.

The difference is that we assume the electron is essentially removed from the atom in the photoelectric effect. Elections are weakly enough bound in a metal for a UV photon to achieve this. But in general, for UV degradation, the UV photon can't actually remove the electron from the molecule. But the photon can energize electrons that lead to degradation reactions.