A series of symmetrical chiral, liquid crystal dimeric molecules possessing ester-linked, biphenyl-naphthyl cores with varied spacer lengths and terminal vinyl groups have been synthesized using Naproxen as the synthetic precursor. The synthesized symmetrical chiral dimers were characterized by 1H NMR spectroscopy, and their liquid crystalline behavior was confirmed by DSC and HOPMstudies. Structural effects on themesomorphic and physicochemical properties were investigated in terms of variation of chiral chain length. The synthesized dimeric compounds exhibited SmX*, SmC*, SmA*, N*, BPI*, and BPII* mesophase sequences. An odd-even effect was observed in the dimers and the duration of the mesophase decreased with increasing spacer length. The synthesized vinyl substituted liquid crystalline dimers are particularly useful in understanding liquid crystal polymorphism and act as model compounds for liquid crystal polymers.