In this study, porous composite materials were prepared from calcium citrate (CC) and polylactic acid (PLA). Scanning electron microscopy (SEM) showed that the prepared composite materials had the uniformly pore distribution and suitable pore size for bone tissue engineering and displayed proper mechanical properties. As confirmed in X-ray diffraction (XRD), SEM and thermal analysis, the lipophilic property of CC had the improved compatibility and uniform dispersion in the PLA matrix. In addition, the prepared materials showed the high mineralization activity and the ability to guide the formation of apatite since the hydrophilicity of CC improved the wettability of the composite materials. In vivo animal experiments showed that the material was nontoxic and had good biocompatibility. Furthermore, the synergic degradation of CC and PLA effectively neutralized the acidic environment, thus preventing partial inflammation caused by acidic products. CC/PLA composite materials provide a promising new bone repair material for bone tissue engineering.