AbstractLarge bone defects due to accidental injuries and fractures as well as the mismatch between the implant material and the defect site are major problems in biomedicine. Bone tissue engineering offers a solution to this problem. In this paper, a series of three‐dimensional porous composite scaffolds with shape memory were prepared using polycaprolactone and polytetrahydrofuran as soft segment materials, hexamethylene diisocyanate as hard segment materials and amorphous calcium phosphate/calcium citrate (CAP) as inorganic fillers. The scaffolds have tunable mechanical properties, melt temperature, surface wettability, a pore size range of 100–800 μm and a high degree of connectivity. In vitro mineralization showed good mineral deposition and energy dispersion spectrometer displayed uniform distribution of Ca and P elements on the surface. The composite scaffold exhibited good shape memory properties at 37°C. The shape fixation rate (Rf) and shape recovery rate (Rr) were maintained at 94.1% and 94.4% after five compression cycles. The resulting scaffold promoted MG63 cell proliferation to some extent. The scaffold is expected to be used clinically for the treatment of large bone defects.