Based on a high power CO2 laser beam passing by an integral mirror, the bioceramic coatings of gradient composition were designed and fabricated on titanium alloy substrate (Ti-6Al-4V). The relations among laser processing parameters, microstructure and thermal behavior of the gradient bioceramic coatings were investigated. The morphology of the composites was observed by scanning electron microscope (SEM). Phase composition of the coatings was analyzed by X-ray diffraction (XRD). And the thermal behavior of raw powders was evaluated through thermal gravimetry and differential scanning calorimetry (TG-DSC) test. The results demonstrated that the bioceramic coatings were metallurgically bonded to the titanium alloy substrate. The bioceramic coatings contained such bioactive phases as HA and β-TCP, which offered an advantageous condition for osseo-connection. The DSC thermograms showed the endothermic peaks at different temperature, which resulted from the different transitions process, respectively. Furthermore, the DSC results were in accordance with TG data of the powders and showed that with the increasing temperature the weight of sample accordingly decreased.