A series of novel azo-containing twin liquid crystalline (LC) epoxy monomers were cured with anhydrides without extra catalyst, and the curing kinetics was investigated by non-isothermal differential scanning calorimetry (DSC) technique. The results showed that the effect of phase behavior on activation energy (Ea) was enormous, which increased first and then decreased quickly with the curing reaction processing. The chemical kinetic control and diffusion-control mechanisms dominate the curing together, which gives large values of Ea. Azo group also served as a catalyst to accelerate the curing reaction. The curing mechanism was confirmed by the UVVis spectra of azo-doped curing system in which the absorbance values at 366 nm and 475 nm changed with the curing reaction processing. POLYM. ENG. SCI., 2012. (C) 2012 Society of Plastics Engineers