Novel Poly(l-lactic acid) (PLLA)/ Multi-walled carbon nanotubes (MWNTs)/ hydroxyapatite (HA) nanofibrous scaffolds with high porosity and well-controlled pore architectures were prepared via electrospinning techniques. The structure, morphology, molecular weight change of the scaffolds were investigated using scanning electron microscopy (SEM). The results noticed that the average diameter of hybrid nanofiber was similar to that of PLLA/HA fiber, but the surface of hybrid fibers was much coarser because of the introduction of MWNTs nano-particles. The biocompatibility of the scaffold has been investigated by human Dental Pulp Stem Cells (DPSCs) cell culture on the scaffold. The preliminary results showed that cells were well adhered and proliferated on the hybrid scaffolds as well as PLLA/HA fibers. Based on the experimental observations, the aligned nanofibrous PLLA/ MWNTs /HA scaffold could be used as a potential candidate scaffold in dental tissue engineering.