A new surface modification method by modifying low molecular weight ploy (L-lactide) (LMW PLLA) onto the β-tricalcium phosphate (β-TCP) superfine particles has been developed. The surface-modified β-TCP is characterized by FT-IR, XRD, digital microscope and contact angle measurement, et al. FT-IR spectra confirmed that LMW PLLA was connected onto the β-TCP surface through ionic interaction. XRD results indicated that the LMW PLLA did not affect the crystalline form of β-TCP, but the XRD patterns of the p-β-TCP showed a little difference with β-TCP. The p-β-TCP particles could be dispersed uniformly in dichloromethane. In contrast, unmodified β-TCP particles are apt to agglomerate after dispersed into dichloromethane. Wet angle measurement showed that hydrolyzed LMW PLLA significantly improves hydrophobicity of modified β-TCP particles. For the preparation of composites, PLLA was mixed with β-TCP and p-β-TCP, respectively, in a ratio of 85/15 (w/w) and moulded into tensile test specimens. Tensile tests showed that mechanical properties were improved, scanning electron microscopy (SEM) exhibited that modified β-TCP is an effective approach to prepare a homogeneous composites, moreover, it indicated a better interfacial phase interaction in the composite with the p-β-TCP. Chemical bonds between filler and PLLA matrix are assumed to be formed by ionic interaction.