The thermotropism of 1-n-alkyl-(4-methyl and 4-tolyl)pyridinium bromides were compared for alkyl chain lengths ranging fromn= 12 to 22 carbons. A smectic A mesophase is present in both series for the longer chain compounds,n≥ 16, with the clearing temperature being similar for both series but increasing rapidly with chain length. The series with the elongated mesogen also possesses an ordered mesophase identified as smectic G. The transition between this mesophase and the SAor isotropic phase in the 4-tolyl series, and the transition to and from the crystalline phase in both series, are affected relatively little by the alkyl chain length. It seems that the SAmesophase is governed primarily by the amphiphilic character of the substances, whereas elongation of the ionic head group is responsible for the appearance of a more ordered mesophase at intermediate temperatures.