Poly(L-lactic acid)/hydroxyapatite hybrid nanofibrous scaffolds were prepared via electrospinning. The structure and morphology of the scaffolds were investigated using scanning electron microscopy, differential scanning calorimetry and Fourier transform infrared spectroscopy. The experimental results showed that the average diameter of hybrid nanofiber was similar to that of pure poly(L-lactic acid) fiber, but a new surface bonding (COO-) was formed in hybrid nanofiber which made the surface of the fiber coarse. The weight loss and water uptake of pure poly(L-lactic acid) scaffolds increased continuously and the viscosity-average molecular weight decreased in the phosphate buffer solution as time passed, while those of hybrid scaffolds were very much slowed down because the dissolving of hydroxyapatite particles acted as a physical barrier and blocked off the entry of water. The biocompatibility of the scaffold has been investigated by human osteosarcoma MG-63 cell culture on the scaffold. The preliminary results showed that cells were well adhered and proliferated better on the hybrid scaffolds than pure scaffolds.