Acidolysis polymerization has been used to prepare phenol-derived polymers such as liquid crystalline (LC) polymers, and is catalyzed by mildly-alkaline salts. The catalytic effects of hydrotalcites (HTs), which are natural alkalescent minerals with controllable basicity, are investigated on the acidolysis copolymerization of coumarates such as p-coumaric acid and caffeic acid. As a result, the LC copolymer prepared in the presence of HT with a Mg/Al ratio of 3 shows higher molecular weight values than copolymers prepared in the presence of any other alkalescent salts. On the other hand, the copolymers prepared in the presence of HTs show a clear LC state where the polymer chains are oriented on the surface of the glass fibers. The resin, which is oriented by glass fiber fillers aligning along its longitudinal axis and is annealed at 300 °C for 20 min, shows a softening temperature of 305 °C while keeping a high mechanical strength of 85 MPa and a high mechanical modulus over 1 GPa.