Five series of 3-hydroxy-5-cholenic acid derived steryl benzoates and cinnamates were synthesized and their phase transition properties were characterized by differential scanning calorimetry and polarizing optical microscopy. Their thermal phase behavior is significantly different from that of the cholesterol-based analogues because of the polar side chain. The effects of the fluorination pattern of the phenyl group, the trans-double bond in the acyl moiety, the unsaturated or saturated B-ring, and the length of the terminal alkoxy group are discussed. Two cholesterol-derived cinnamate series were also prepared for comparison.