Degradation reaction paths starting from riboflavin (RF) were investigated using DFT (density functional theory) as the first attempt to reveal their elementary processes. Photochemical reactions were followed in the lowest triplet spin state, “(T)”. Two intermediates [Int1(T) and Int2(T)] were found in the course, RF(T) → FMF (7,8-dimethyl-10-formylflavin, T). From FMF(T), there are two degradation channels. Release of ketene(T) and carbon monoxide leads to LC (lumichrome, S0) and LF (lumiflavin, T), respectively. The base-catalyzed (ground state) degradation of FMF was investigated with HO–(H2O)3. The Grotthuss-type proton transfer along hydrogen bonds controlled the degradation reaction. All the transition states of cleavage of CC and CN covalent bonds were determined, and the degradation mechanism was clarified.