Effects of chemical structure changes on the thermal, mechanical, and crystalline properties of rigid rod epoxy resins have been studied for azomethine epoxy, biphenol epoxy, and tetramethyl biphenol epoxy. Rigid rod epoxies have exhibited better properties than those of the flexible bisphenol A epoxy. The chemical structures of both rigid rod epoxy and curing agent control the properties of cured rigid rod epoxies. When a flexible curing agent (methyl cyclohexane 1,2-dicarboxylic anhydride) was used, the chemical structure of rigid rod epoxy has dominated effects on the properties. Thus, the azomethine epoxy has shown the best thermal and mechanical properties among three rigid rod epoxies. While a rigid curing agent (sulfanilamide) was used, the physical properties of cured epoxies are not only dependent on the chemical structures of epoxies but also on the ease of formation of ordered network. Among the cured rigid rod epoxies, only the biphenol epoxy cured by sulfanilamide exhibits a liquid crystalline network. It has the highest glass transition temperature (219 degrees C) and the lowest coefficient of thermal expansion (20.8 mu m/m degrees C). However, the most thermal stable system is azomethine epoxy cured with sulfanilamide. It has a weight; loss (39%) at 450 degrees C. Their excellent thermal and mechanical properties of rigid rod epoxies are useful in composites, printed wiring boards, integrated circuit encapsulations, etc.