A new homologous series of mesogenic dimers with an odd-numbered flexible spacer is presented. It is shown that the short-chained members of the series form a SmC phase, only whereas the longer-chained homologues exhibit a SmA phase. The layer spacing of the SmC phase was found to be about the half of the molecular length. This result and the occurrence of singularities with s = 1/2 or s = 3/2 in the schlieren texture point to an intercalated structure. The electro-optical switching of the SmC phase can be attributed to a dielectric transition.