The synthesis and characterization of 10 new rod-shaped substituted benzoates possessing the 4-(2-trimethylsilyl)ethynyl group in terminal phenyl position is reported employing the simple and efficient Sonogashira cross-coupling and DCC esterification. 4-Dodecylbiphenyl-4-carboxylic(2-trimethylsilylethynyl)-phenyl ester (3i), 4-(4-hexadecyloxybenzyloxy) carboxylic-4-trimethylsilanylethynyl-phenyl ester (3j), and 1,4-bis(4-(pentyloxy)phenyl)buta-1,3-diyne (7) compounds were evaluated for liquid crystal property. [Supplemental materials are available for this article. Go to the publisher's online edition of Molecular Crystals and Liquid Crystals to view the free supplemental file.]