Liquid crystalline alkoxy stilbenes with chlorosilyl end groups were synthesized for the first time. The chlorosilyl end groups, even though bulky, tend to promote smectic mesophase due to their high polarity. The long range dipole-dipole intermolecular attractive forces overpower repulsive steric interactions. Theoretical calculations show the dimers from these chlorosilyl precursors to prefer bent conformation over extended one and thus they prove to be good models for side chain polysiloxanes.