Abstract: A homologous series of cholesteryl 4'-alkyloxybiphenyl-4-carboxylates (C_nH_2n+1OC₆H₄ C₆H₄COOCh, where Ch = cholesteryl) possessing different length of alkyl chain (n = 6, 8, 10, 12, 14, 16, 18) were synthesized. Phase transition temperatures and thermal parameters were obtained from differential scanning calorimetry. Observation under optical polarizing microscope revealed all the members of the series possessing SmA property. Additional mesophase was observed for lower members whereby the C6-14 derivatives displayed fan-shaped and oily streaks textures of cholesteric phase. The influence of structural changes on the mesomorphic properties is discussed.