We describe an experimental and theoretical consideration of photoexcited proton transfer in a poly(4-vinyl pyridine)/pyridine gel. Evidence was found for two states of a multiple state process analyzed by DFT modeling. According to the latter, following irradiation at 385 nm, the proton donor is the CH group of the polymer main chain and the proton acceptor is the nitrogen of the polymaric pyridine side chain. Proton transfer is made possible through the assistance of a mobile pyridine solvent molecule acting as a transfer vehicle. Proton transfer promotes both a geometrical rearrangement of the vinyl side chain as well as electronic density redistribution. The photoproduct intermediate - the hydrogen-bonded complex between the protonated solvent pyridine molecule and the deprotonated polymeric pyridine side chain - is identified by its Curie law magnetic susceptibility, ESR spectrum, and fluorescence lifetime measurements. The proton transfer from the nitrogen of the solvent pyridine molecule to the pyridine side chain nitrogen, producing pyridinium, is a thermodynamically favorable relaxation process and occurs without an energy barrier. The protonation of nitrogen on the polymeric side chain was detected by solid state NMR spectroscopy performed on a 15N-polymer enriched gel. The calculations and experimental data suggest a central role for the gel solvent molecule as a catalytic agent and proton transfer vehicle. The process suggested by DFT modeling may have relevance for photosensitive devices in part due to the fact that we have been able to show that long-lived paramagnetism may be included among the inducible properties of soft polymer gels.