The bioactivity of poled piezoelectric PLLA membrane was investigated by studying the calcium phosphate formation in vitro using a biomimetic method. Samples (φ10mm) were poled under DC electric field of 8~l0kV/cm at 70°C for 30 min followed by cooling under the electric field. Surface chemistry of the samples before and after poling treatment was studied by X-ray photoelectron spectroscopy (XPS). Poled/unpoled samples were immersed in supersaturated calcification solution (SCS) for periods up to 24 h (36.5°C). The surface morphology and composition of the soaked samples were evaluated by using scanning electron microscope (SEM) and X-ray diffraction analysis (XRD). Poled samples showed two different charged surfaces, negatively-charged surface (N-PLLA) and positively-charged surface (P-PLLA). On the N-PLLA surfaces, SEM together with XRD showed a gradually formed calcium phosphate (Ca-P), while no obvious Ca-P on either P-PLLA or unpoled samples was observed. This study demonstrated that poled piezoelectric PLLA substrates induce substantially higher level of Ca-P formation than electrically neutral substrates and only N-PLLA, however, can improve Ca-P formation after immersion in SCS.