Crystal structures have been determined for 4-[(S)-1-methylpentyloxycarbonyl]phenyl, 4-([S)-1-methylhexyloxycarbonyl]phenyl 4′-octyloxybiphenyl-4-carboxylates (1and2, respectively) and (R)-1-methylheptyl 4-(4′-octyloxybiphenyl-4-yloxymethylene)benzoate (3), which have SCA*, SC* and SCA* phases, respectively. All the crystals have a common packing mode with the previously determined structure of 4-(1-methylheptyloxycarbonyl)phenyl 4′-octyloxybiphenyl-4-carboxylate (MHPOBC). Each crystal forms a smectic-like layer structure composed of largely bent molecules with the long alkyl chain of the chiral group almost perpendicular to the core moiety. Differential scanning calorimetry showed that the crystals of1, 2, and MHPOBC, which have a carbonyloxy group as the central linkage between the biphenyl and phenylene moieties, transform to higher temperature solid phases in a similar temperature range (around 60°C). For3, which has an oxymethylene linkage between the biphenyl and phenylene moieties, three kinds of solids were distinguished.