A now series of non-symmetrical dimeric compounds containing two distinct mesogenic groups, 4-(4'-benzyloxy)biphenyl cholesteryl alkanedioates, was prepared in our laboratory. In addition, two symmetrical dimers, dichoresteryl decanedioate and di[4-(4'-benzyloxy)biphenyl] decanedioate, were synthesized, The phase transition behavior of these compounds has been studied by a differential scanning calorimeter and a polarizing microscope. In the case of the symmetrical dimers, dichoresteryl decanedioate gave rise to a monotropic cholesteric phase and di[4-(4 -benzyloxy)biphenyl] decanedioate showed no liquid crystallinity. On the other hand, 4-(4 -benzyloxy)biphenyl cholesteryl decanedioate which is the non-symmetrical dimer gave rise to three liquid crystalline phases in wide temperature range. Moreover, a typical even-odd effect with regarded to the phase transition behavior was observed for the non-symmetrical dimetric compounds.