The antioxidant and prooxidant properties of some B vitamins (BVIT) and vitamin-like compounds (VLC) that are commonly included in multivitamin preparations were investigated. Microsomal lipid peroxidation induced by FeCl3 and ascorbate was dose-dependently inhibited by pyridoxal and pantothenate but was stimulated by thiamin, pyridoxine and carnitine. Among the compounds tested, only pyridoxine and pyridoxal reacted, but rather poorly, with superoxide anions. All test compounds reacted with .OH with second-order rate constants comparable or higher than that for mannitol, as assayed using deoxyribose oxidation by a system containing EDTA-chelated Fe(III), H2O2 and ascorbate. When assayed in the absence of EDTA, pyridoxal showed increased inhibition of deoxyribose oxidation over that in the presence of EDTA, suggesting a potent ability of pyridoxal to bind and deactivate iron. Pantothenate, pyridoxine and myo-inositol appeared to equally inhibit deoxyribose oxidation both in the presence and absence of EDTA. The lack of inhibition on deoxyribose oxidation in the absence of EDTA by thiamin, carnitine and choline may suggest that the .OH-scavenging ability is equalled by the ability of the scavenger-iron complexes to form .OH or other redox active species. However, stimulation of lipid peroxidation by pyridoxine was unexplained and the effect was not attributed to reduction of Fe(III) to Fe(II). This study shows that the radical-scavenging ability of BVIT and VLC did not correlate with their effects on microsomal lipid peroxidation. Moreover, the stimulation of lipid peroxidation by thiamin, pyridoxine and carnitine suggests that supplementation of large amounts of these compounds may not be desirable.