The thermal degradation behavior of blends of poly(aryl ether ether ketone), PEEK, with a thermotropic liquid crystalline polymer (TLCP), Vectra (R), were investigated in an oxidative atmosphere, using thermogravimetric analysis under dynamic conditions. The theoretical weight loss curves of the blends were compared with the experimental curves in order to explain the effect of blending on the thermal stability of the pure polymers. The thermo-oxidative degradation of PEEK/Vectra (R) blends of different compositions takes place in various steps and the characteristic degradation temperatures and the kinetic parameters such as activation energy are strongly influenced by blending. Polymer blends based on this TLCP polymer had not been previously studied from kinetic viewpoint.