Fluoro substitution in thermotropic liquid crystals provides a general way of modifying the properties of a parent system. Transition temperatures, mesophase types and other physical properties can be affected by fluoro substitution, so that frequently the behaviors of the parent compound can be manipulated and improved in a predictable manner. This paper discusses the effects of a fluoro substitution in each side-arm of 1,2,4,5-tetrakis((4-(alkoxy)phenyl)ethynyl)benzenes on the resulting mesomorphic properties characterized by optical polarizing microscopy and differential scanning calorimetry. Without any fluoro-substituted side-arms, longer chain-length leads to a wider nematic temperature range on cooling. Incorporation of a fluoro substitution in each side-arm induces the formation of a lamellar suprastructure, lowers transition temperatures and results in a wider mesophase temperature range on cooling.