The crystal structure of (S)-l-methylheptyl-4'-[4-octyloxy-2-[11-[4-(5-hexylpyrimidin-2-yl)phenoxy]undecanoyloxy)benzoyloxy)biphenyl-4-catrboxylate, which has a relatively wide temperature range of blue phase III on cooling, has been determined. The molecule was found to form a A-shaped structure. We have prepared a homologous series of the chiral oligomers and investigated effects of structure on appearance of the blue phase. All compounds were found to show a phase sequence of Iso-BP-N*-glass on cooling. The structure-property correlations reveal that (1) chirality does not affect on the Iso-BP transition temperature, (2) increasing chirality destabilizes the N* phase, and (3) the longer spacer lowers the BP-N* transition temperature.