The newly built 177 nm all-solid-state deep ultraviolet (DUV) laser photoionization mass spectrometer finds a unique advantage to identify porphyrins that bear ionization energies close to 7.0 eV. We observed dramatic selectivity of tetraphenylporphyrins (TPPs) pertaining to varied photochemical processes initiated by the DUV laser excitation. Single-photon ionization was found dominant for 2H-TPP resulting in a fragmentation-free mass spectrum; photoinduced dehydrogenation was observed for zinc TPP, but both dehydrogenation and demetalation are noted for copper TPP. Along with first-principle calculations, we demonstrate how the photoinduced reactions vary with residual energies of photoionization, highest occupied molecular orbital lowest unoccupied molecular orbital gaps, donor acceptor orbital overlaps, single-step barriers, and whether or not there is a major process of structural rearrangement. It is demonstrated that the rotation of benzene ring under proper laser radiation prompts dehydrogenation process; also, metallo-TPPs do not support direct demetalation, but it is selectively accomplishable along with dehydrogenation and successive hydrogenation processes. These findings not only provide insights into the hydrogen atom transfer in porphyrins initiated by ultraviolet laser but also suggest promising applications of the DUV laser in designed synthesis and chemical modification of porphyrins.