Herein hydroxyapatite (HA) has been synthesized by the nucleation on the surfaces of reduced graphene oxide/silver nanoparticles (rGO/AgNPs) chemisorbed with thioglycolic acid (TGA). The self-assembled monolayer of TGA formed on rGO/AgNPs was immersed in simplified simulated body fluid under gentle growth conditions, forming rGO/AgNPs/TGA/HA biocomposite. The phase structures and functional groups of biocomposite were analyzed by X-ray diffraction spectroscopy, Fourier transform infrared spectroscopy and Raman spectroscopy. Enhanced Raman spectrum of TGA on prepared rGO/AgNPs was obtained with excitation at 633 nm, showing that TGA was chemisorbed on AgNPs through S atom and TGA molecular plane exhibited a tilted orientation with respect to AgNPs. The morphologies of biocomposite were investigated by means of atomic force microscope and transmission electron microscope coupled with energy dispersive spectrum. Analysis shows that the AgNPs uniformly distributed on the rGO nanosheets with the size of about 15-20 nm and HA formation initiated through Ca2+-adsorption upon complexation with -COO- groups of TGA on AgNPs. The results obtained indicated that the rGO/AgNPs/TGA/HA biocomposite may have immense potential application in bone tissue engineering fields for its outstanding and stable activities. (C) 2013 Elsevier B.V. All rights reserved.