The photoisomerization dynamics of N-methyl-2-pyridone (NMP) dissolved in CH3CN have been interrogated by time-resolved electronic and vibrational absorption spectroscopy. Irradiation at two different wavelengths (330 or 267 nm) prepares NMP(S-1) molecules with very different levels of vibrational excitation, which rapidly relax to low vibrational levels of the S-1 state. Internal conversion with an associated time constant of 110(4) ps, leading to reformation of NMP(S-0) molecules, is identified as the dominant (>90%) decay pathway. Much of the remaining fraction undergoes a photoinitiated rearrangement to yield two ketenes (revealed by their characteristic antisymmetric C=C=O stretching modes at 2110 and 2120 cm(-1)), which are in equilibrium. The rate of ketene formation is found to be pump-wavelength dependent, consistent with ab initio electronic structure calculations which predict a barrier on the S1 potential energy surface en route to a prefulvenic conical intersection, by which isomerization is deduced to occur. Two kinetic models-differentiated by whether product branching occurs in the S-1 or S-0 electronic states-are presented and used with equal success in the analysis of the experimental data, highlighting the difficulties associated with deducing unambiguous mechanistic information from kinetic data alone.