The effect of the heat-treatment on the calcium phosphate deposited on Ti-6Al-4V substrate by an electrolytic process has been investigated. The calcium phosphate were deposited in a 0.04M Ca(H2PO4)2･H2O (MCPM) solution on Ti-6Al-4V substrate at 60 °C, 10V and 80 Torr for 1h, and calcined at different temperature for 4h. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to characterized the deposited samples. The XRD pattern of as-deposited sample contain the phase of dicalcium phosphate (DCPD) and HAP. When calcined at 400 °C for 4 h, the DCPD phase is vanished and HAP becomes the major phase. The XRD pattern reveals that the intensity of HAP and Ca2P2O7 (CPP) decreases, but the β-TCP, CaO and rutile TiO2 also shows up.