A new series of liquid crystal tetramers, which contained four biphenyl groups joined by three flexible spacers, was prepared. The tetramers showed nematic and/or smectic phases. The melting points, the nematic-isotropic transition temperatures, and the entropy changes associated with the nematic-isotropic transition showed a remarkable odd-even effect as the length of the spacers was varied, in which the even members exhibited higher values. The transition properties of the liquid crystal tetramers were compared with those of liquid crystal dimers and trimers, which consist of two and three biphenyl groups.