Effects of 3-substituted pyridinium compounds (1-benzyl-3-carbamoylpyridinium chloride (I) and 1-benzyl-3-carboxypyridinium chloride (II)) on the electrocrystallization of zinc from an alkaline cyanide bath have been studied by electrochemical methods, microscopic observation and X-ray diffraction. The zinc deposit from an alkaline cyanide bath exhibited a preferred orientation with the (1120) plane parallel to the surface, and its cross section showed a fibrous structure. On the other hand, the zinc deposit from the bath containing pyridinium (I) exhibited the (1010) and (1011) planes oriented with the surface, and the zinc deposit from the bath containing pyridinium (II) exhibited a preferred orientation with the (1010) plane. Their cross sections did not show fibrous structures but textures with fine grains.