The formation and reactivity of the triplet state and free radicals of mefloquine hydrochloride (MQ) have been investigated by pulse radiolysis and flash photolysis. The excited triplet, cation radical and anion radical have been produced and their absorption characteristics determined. The triplet-triplet absorption spectrum of MQ showed a maximum at 430 nm, with a molar absorption coefficient of 3600 M(-1) cm(-1) and the quantum yield for intersystem crossing was determined to be close to unity. Deactivation of the triplet, in the absence of oxygen, led to the formation of MQ cation and/or anion radicals. The molar absorption coefficient of the cation radical at 330 nm was determined to be 2300 M(-1) cm(-1), whilst that for the anion radical was 2400 M(-1) cm(-1) at 620 nm and 3600 M(-1) cm(-1) at 350 nm. The molar absorption coefficients of the proposed neutral radical at 320 nm and 520 nm were 4000 M(-1) cm(-1) and 1300 M(-1) cm(-1) respectively. The quantum yield for the formation of singlet oxygen, sensitized by MQ triplet, was determined to be close to unity. Aqueous solutions of MQ were found to photoionize to yield hydrated electron and cation radical of MQ in a biphotonic process. The influences of pH, buffer concentration, oxygen concentration and addition of sodium azide on the formation and reactivity of the transients were evaluated. The reactions between MQ and solvated electrons and superoxide anion were also studied.