Organic polymer–hydroxyapatite (HA) hybrid was expected as a promising bone substitute. In this work, poly(vinyl alcohol) (PVA) was used as a polymer substrate and the PVA-HA hybrid was prepared by a biomimetic process. The resultant PVA-HA composites were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis and scanning electron microscopy. It was found that HA could deposite on PVA surface when PVA soaked in water for a little swelling and then was carried out CaP treatment previously. The formed HA showed bone-like structure and had a good interaction with PVA substrate. The resultant hybrid might exhibit good osteoconductivity and biocompatibility, and could be expected as a useful scaffold for bone tissue regeneration.