RF sputtering process was applied to produce thin hydroxyapatite(HAp) films on Ti-6Al-4V alloy substrates. The effects of different heat treatment conditions on the chemical composites between HAp thin films and Ti-6Al-4V alloy substrates were studied. After deposition, the HAp thin films were heat treated for 1h at $400^{circ}C,;600^{circ}C;and;800^{circ}C$ under the atmosphere, and analyzed O/M, FESEM-EDX and ESCA, respectively. Experimental results represented that interface of HAp thin films and Ti-6Al-4V alloy substrates was composed Ti-OH, TiO, TiN, $Al_2O_3,;V_2O_3,;VO_2$. pyrophosphate and decreased carbide followed by the increase of heat treatment temperature.