A sterically hindered cyclic amine, 4-hydroxy-2,2,6,6-tetramethylpiperidine (HTMP), is converted to the corresponding aminoxyl radical (nitroxide radical), 4-hydroxy-2,2,6,6-tetramethyl piperidine 1-oxyl (TEMPOL radical) as a result of a photocatalytic reaction in TiO2 aqueous suspension. The time profile of the radical formation and the effect of additives, such as SCN-, I-, methanol, and H2O2, on the initial formation rate were measured in order to elucidate the reaction mechanism. The experimental observations indicated that the direct photocatalytic oxidation of HTMP followed by reaction with O-2 is the dominant process in the formation of TEMPOL radicals. Electrochemical measurements showed that HTMP is oxidized at 0.7 V (vs NHE), which is consistent with the proposed mechanism. The possibility of other processes, involving reactions with singlet molecular oxygen, superoxide radical, and hydroxyl radical, were excluded from the reaction mechanism.