Hydroxyapatite (HAp) films were deposited on a β-type titanium alloy, Ti-29Nb-13Ta-4.6Zr (TNTZ), by metal organic chemical vapor deposition (MOCVD) in order to improve its hard-tissue compatibility. The surface morphologies of TNTZ substrates were changed by acid treatments and mechanical polishing prior to the HAp film deposition. The adhesive strength of the HAp films formed on TNTZ substrates treated with an HF solution increased to twice that of the HAp film deposited on a TNTZ substrate with a mirror-like finish. Complex microstructures with deeply etched grain boundaries, formed on the TNTZ substrates after immersion in the HF solution, were responsible for the increase in the adhesive strength of the HAp film caused by an interlocking effect. The HAp films on TNTZ substrates treated with a H(2)SO(4) solution exhibited lower adhesive strength than HAp films on TNTZ substrates treated with HF solution, regardless of the surface roughness of the substrates. Additionally, acid treatments using HNO(3) and H(2)O(2) solutions did not change the surface morphologies of the TNTZ substrates. The complex microstructures with deeply etched grain boundaries and nanosized asperities formed on the TNTZ substrates are important factors in the improvement of the adhesive strengths of HAp films deposited on TNTZ substrates.