Porous polyvinyl alcohol/β-Tricalcium phosphate/carbon nanotubes (PVA/β-TCP/CNT) composites were prepared by freeze-thaw method, and the effects of CNT addition on the porosity and mechanical properties of CP/CNT composite materials were investigated. The results show that adding an appropriate amount of CNT can effectively reduce the pore size and porosity of PVA/β-TCP/CNT porous composites ensure the formation of a denser porous structure in the porous polyvinyl alcohol composites. When the CNT addition amount is 0.3%~0.5%, the porosity of the composites is the lowest, about 82%. After adding CNT, the elastic modulus and tensile strength of PVA/β-TCP/CNT porous composites were significantly improved, and the swelling of PVA/β-TCP/CNT porous composites is significantly decreased. When the CNT addition is 0.3%, the elastic modulus and tensile strength of the composites reach 2 245.08 MPa and 6.61 MPa, respectively. The prepared PVA/β-TCP/CNT porous composites can meet the requirements of medical biomaterial polymer scaffolds.