The oxyanionic copolymerization of ε-caprolactone (CL) and glycidyl methacrylate (GMA) was employed to synthesize a biodegradable vinyl-functional polymer, which subsequently performed as macro-crosslinker for the biodegradable polymeric porous materials. A vinyl-termed poly (2- (dimethylamino) ethyl methacrylate) (PMDMAEMA) was also synthesized to endow the porous materials functionality. The structures of macro-crosslinker and macro-monomer were confirmed by nuclear magnetic resonance spectrometer (NMR) and Fourier transform infrared spectroscopy (FT-IR). The synthesized polymeric porous materials were analyzed by scanning electron microscope (SEM). The results show that the molecular weight for the synthesized macro-crosslinker with 20% unreacted vinyl groups was 8100. When the mole ratio of macro-crosslinker to monomer is 1/10, the resulted polymeric porous materials were of uniform pores with the diameter of 20～22 nm. Using PDMAEMA as macro-monomer, the diameter of pores wall is between 10～15 μm, and the size of holes is between 5～8 μm. This polymeric porous material can be partially hydrolyzed in alkaline solution.