Biodegradable β-tricalcium phosphate (β-TCP)/poly (lactide-co-glycolide) (PLGA) composites were synthesized by in situ polymerization with microwave energy. The influence of the β-TCP content in β-TCP/PLGA composites on the molecular weight, crystallinity, microstructure, and mechanical properties was investigated. As the molecular weight of composites decreased, the β-TCP content increased up to 10 wt%, while further raising of the β-TCP content above 10%, the molecular weight increased with increasing β-TCP content. This behavior may be ascribed to the superheating effect or nonthermal effect induced by microwave energy. It was found that the bending strength and Young’s modulus of the β-TCP/PLGA composites were proportional to the molecular weight of PLGA. The bending strength of the β-TCP/PLGA composites ranged from 18 to 38 MPa, while Young’s modulus was in the range from 2 to 6 GPa.