This study is to develop a novel method for preparation of the chitosan scaffold having interconnected open pore structure and controlled pore distribution. For this, the effects of addition of non-solvent on chitosan solution were estimated. The porous scaffolds were typically prepared by solid-liquid separation and subsequent sublimation of solvent. Alcohol was used as non-solvent for chitosan. The difference of freezing temperature of each of the components induced the liquidliquid and the liquid-solid phase separation via demixing solution (solvent/non-solvent/chitosan). The morphology, heterogeneous pore distribution and mechanical properties of the scaffolds were examined. The addition of non-solvent in chitosan solution was to make the controlled homogeneous micropores and improved interconnectivity between pores without any surface skin layer. For control chitosan scaffold, the pore size was mainly about 80~100 μm. On the contrary, Pore diameters could be controlled mainly within the range 30~100 μm, with a variation of solvent/non-solvent ratio. The number of minute pore (4~25 μm) over chitosan scaffold increased with increasing ratio of non-solvent. New prepared scaffold exhibited larger value of breaking elongation, more elasticity, but less tensile strength than that of control scaffold.