Two different reaction types for the photolysis of pyridoxine-aromatic ring-opening and photodissociation-have been studied in the Density Functional Theory (DFT) framework. Our results show that neither photolytic ring-opening, dehydroxymethylation, demethylation nor dehydroxylation from the aromatic ring can be induced spontaneously in UV-irradiated pyridoxine, due to the high barriers along the reaction coordinates in the excited states. However, the simultaneous dehydroxylation of the C4-bound hydroxymethyl group and dehydrogenation of the ring bound hydroxyl substituent, selectively generating ortho-quinone methide and water, does occur after UV exposure. The findings correlate very well with available experimental data. The geometries of pyridoxine, its various transition states and products are optimized in the ground and first excited states in vacuum within the TD-DFT formalism.