We have synthesized and characterized five members of a homologous series of side chain polymers of hydroxypropyl cellulose esters obtained by homogeneous esterification with 6-[4′-(ethoxycarbonyl)biphenyl-4-yloxy]hexanoic acid. Two acylation procedures were studied. One procedure involved the acid chloride derivative and the other one was the activation of that acid with N,N′-carbonyldiimidazol. The second method yielded esters with higher degree of substitution, DS¯. The esters, with DS¯ ranging from 26 to about 66%, were characterized by FTIR, NMR, solution viscometry, TGA, DSC, polarized optical microscopy, and X-ray diffraction, in order to study the effect of the degree of substitution on the hydrophobicity, on the transition temperatures and on their potential liquid crystal properties. It has been found that the hydrophobicity and the transition temperatures of the HPC derivatives are very much dependent on the degree of acylation. The esters with high DS¯ values showed liquid crystal properties.