A novel nano-hydroxyapatite/chitosan (n-HA/CS) composite scaffold with high porosity was developed by a new method of emulsion-foaming/freeze-drying process and was characterized by means of infrared spectroscopy (IR), scanning electronic microscopy (SEM) and universal material testing machine. In addition, the porosity and density of the scaffold were also calculated. IR result shows that the characteristic absorption peaks belonging to both CS and HA are present in their composite, and the slight band-shifts and peak-decrease suggest that some interactions have taken place between the two phases of CS and n-HA in the composite. SEM photo displays that, with the dosage increase of Tween-80, the prepared scaffold shows highly porous and interconnected structure, in which macropores and micropores coexist. The calculated data demonstrate that the porosity of the scaffold is proportional to the content of the emulsifier, while the compressive strength is inversely. When 15wt% emulsifier used, the porosity of the scaffold can be up to 90% and the density is 0.453g/cm3, while the corresponding compressive strength is about 2.4MPa. The newly developed n-HA/CS composite scaffolds may serve as a good 3-D substrate for cell attachment and migration in bone tissue engineering.