A well-distributed nano-silver hydroxyapatite composite has been successfully prepared by a one-pot synthesis method. Hydroxyapatite was separately synthesized by a sol-gel method, then impregnated with silver nanoparticles with the mediation of Uncaria gambir Roxb. leaf extract in the presence of three kinds of alkanolamine compound; monoethanolamine (MEA), diethanolamine (DEA), and triethanolamine (TEA) as capping agents. The effect of different capping agents on the properties of the silver nanoparticles and the nano-silver hydroxyapatite composite were studied. UV–visible spectrophotometer analysis exhibited absorbance peaks at 402–439 nm which specifically corresponds to spherical silver nanoparticles. Higher optical absorbance was observed in TEA-capped silver nanoparticles, than in DEA and MEA-capped ones. X-ray diffraction (XRD) analysis showed a highly crystalline hexagonal structure for hydroxyapatite and no detected metallic silver. However, the presence of 1.65% silver was confirmed by energy dispersive x-ray (EDX) spectroscopy analysis. Transmission electron microscopy (TEM) analysis revealed spherical silver nanoparticles with a size range of 2–62 nm (smallest mean diameter of 2 nm) adhered to the hydroxyapatite surface. The TEA capped impregnated silver nanoparticles were the smallest, corresponding to the best capping performance, followed by those capped by DEA and MEA. Small-sized nanoparticles on hydroxyapatite are beneficial for highly antibacterial bone implants.