Regular and highly interconnected macroporous poly(L-lactic acid) (PLLA) scaffolds with pore size of 10∼300 ㎛ were fabricated through thermally induced phase separation of a PLLA-dioxane-water ternary system in the presence of a small amount of Pluronics. Addition of Pluronics to the ternary system raised the cloud-point temperature curve in the order of P-123< F-68< F-127. The Pluronics act as nuclei for the phase separation. This assistance is enhanced with increasing length of the hydrophilic PEO blocks in the Pluronics molecules. Liquid-liquid spinodal phase separation was induced at higher temperatures in the systems containing Pluronics because the spinodal region is raised to higher temperature. The absorption of Pluronics onto the interface stabilizes a macro scale structure and increases the interconnection of pores.