C HITOSAN/hydroxyapatite (CS/HA) nanocomposites have been widely fabricated for potential use in bone defects due to their high biocompatibility and similarity to the natural bone. In the current study, HA nanocrystals were prepared by co-precipitation method in CS which was initially dissolved in different concentrations of acrylic acid and acetic acid (2 and 4 %). The effect of chitosan solvents on the morphology of HA nanocrystals, the crystallite sizes, and the physical binding with CS were investigated by different techniques including Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscope (TEM). The FT-IR and XPS results showed that the interaction between CS and HA in the nanocomposites is predominantly dependent on the type of solvent used to dissolve CS. When acetic acid was used, the interaction between CS and HA was stronger when compared to acrylic acid. Quantitative XPS results showed that the atomic percentage of nitrogen (N1s) of the amine groups of CS was less in the case of the composites prepared after dissolving CS in acrylic acid compared to acetic acid. The amine groups of CS (−NH 2 ) can start the nucleation of HA crystals and remain bounded to the surface of the grown crystal through chelation with calcium ions on the crystal facets. In both organic solvents, HA crystals were found to grow along their c-axis direction into rodshape but the growth in the width was more restricted in case of acetic acid. The results in the current study indicated that the type of CS solvents is determining the strength of the physical interaction between the CS and HA. This might be a crucial factor to control and enhance the mechanical and the biological behaviors of the nanocomposites.