The implantation of bioactive composites for bone repair applications has recently gained the attention of many research groups. The present paper introduces a method for grafting of polyvinylpyrrolidone on the surface of hydroxyapatite (CaHAp) microcrystals by wet precipitation method to manufacture new composite scaffolds with suitability for bone tissue engineering. After grafting with the polymer, the degree of CaHAp crystallinity decreased, and its thermal behavior changed indicating a strong interaction between them. Homogenous clusters of CaHAp particles within the polymeric matrix were observed in combination with an increase in the roughness of the resulting structures. Bioactivity of the composites was tested using MTT assay; a higher viability of the seeded cells was observed relative to those cultured with CaHAp powder.