The paper presents the synthesis and mesomorphic behavior of two new series of bent core liquid crystalline compounds based on a 1,3-dihydroxybezene core and containing a cholesteryl 6-oxyhexanoate wing. The two series were obtained by the esterification of the cholesteryl 6-(3-hydroxyphenoxy)hexanoate core with some 4-((4-(n-alkyloxy)phenyl)azo)benzoic acids (n-alkyl = n-hexyl ÷ n-dodecyl) or 4-(4-(n-alkyloxy)benzoyloxy)benzoic acids (n-alkyl = n-hexyl ÷ n-decyl). The esterification reactions were performed via the corresponding acyl chlorides or with the DCC / DMAP system. All the synthesized compounds evidenced enantiotropic liquid crystalline properties, with smectic type textures, when investigated by means of differential scanning calorimetry and polarized optical microscopy. Isotropisation and isotropic to liquid crystal transitions were relatively low (between 89 ÷ 1460C). The compounds containing the azo-aromatic linking group presented the largest range of stability of the mesophases (between 42 and 870C). All the investigated compounds were thermally stable in the existence range of the mesophases.