Polycaprolactone/chitosan (PCL/CS) porous composite scaffolds were prepared by solution phase separation method, and the scaffolds were further enhanced by filling with nano-hydroxyapatite/polyvinyl alcohol (n-HA/PVA) composite slurry to prepare n-HA-PVA/PCL-CS composite porous scaffolds through slurry centrifugal filling technique. The morphology, microstructure, component, porosity and mechanical property of the scaffolds were characterized using scanning electron microscope, X-ray diffraction, Fourier transform infrared spectroscope, elemental analyzer and material test machine. The results show that PCL/CS scaffolds have mutual transfixion porous structure just like honeycombs. The porosity of the scaffolds can achieve 60-80%. As the content of CS increases, the porosity increases while the compressive strength decreases. After filled with HA/PVA composite slurry, the porosity of n-HA/PCL-CS composite scaffolds decreases, but still greater than 60%, while the compression modulus can increase to 25.7 MPa.