Bone defects remains a challenge for surgeons. Bone graft scaffold can fill the defect and enhance the bone regeneration. Demineralized bone matrix (DBM) is an allogeneic bone graft substitute, which can only be used as a filling material rather than a structural bone graft. Coating of the scaffolds with nanoscale DBM may enhance the osteoinductivity or osteoconductivity. Herein the lyophilization method is presented to coat the nano‐DBM on surface of the porous polycaprolactone (PCL)/β‐tricalcium phosphate (β‐TCP) scaffolds fabricated by 3D printing technology. The morphology, elastic modulus, in vitro cell biocompatibility, and in vivo performance are investigated. Scanning electron microscope (SEM) shows DBM particle clusters with size of 200–500 nm are observed on scaffolds fibers after coating. MC3T3‐E1 cells on nano‐DBM coated PCL/β‐TCP scaffold show better activity than on PCL/β‐TCP scaffold. In vivo tests show better infiltration of new bone tissue in nano‐DBM coated PCL/β‐TCP scaffold than PCL/β‐TCP scaffold via the interface. These results show the presence of nano‐DBM coating on PCL/β‐TCP scaffold could enhance the attachment, proliferation, and viability of cells and benefit for the new bone formation surrounding and deep inside the scaffolds. Nano‐DBM could potentially be used as a new kind of biomaterial for bone defect treatment.