Developing of a surface hybrid calcium phosphate-degradable polymer materials is always attractive since it could have high bone bonding ability and proper mechanical properties as natural bone substitute. In this article, a solution blending method was used to make the poly-[(3-hydroxybutyrate)-co-(3-hydroxyvalerate)] (PHBV)/collagen composite with high surface calcium apatite deposition capability. Before the blending, the pseudo ternary phase diagram of CH3COOH-CHCl3/PHBV-H2O/collagen at 20 degrees C was plotted. Three compositions selected from the homogenous zone in the diagram were chosen to fabricate the PHBV/collagen composites. Water contact angle, water absorbance ratio, and FTIR spectra showed the collagen contents in the final composites increased with its original blending ratio. The composite with the highest collagen content was chosen for the biomineralization experiment in simulated calcium solution (SCS). Scanning electronic microscopy showed the morphology of the deposition changing from porous structure to plate structure. The FTIR spectra displayed the precipitate was calcium phosphate containing collagen content. The X-ray Diffractometer spectra displayed that the precipitate has the similar characteristic peaks as calcium apatite and the crystalline increased with the biomineralization time. The concentration of calcium and hydrogenphosphate ions in the SCS monitored in the first 4 h decreased to 29.5 and 1.8 ppm, respectively. The Ca/P of the precipitate stabilized at 1.3 in the first 4 h. The FTIR spectra showed that the amide absorption band shifted to low wavelength, which was caused by the electrostatic force between the calcium ions and the amide bond p-pi conjugation system. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 112: 963-970, 2009