Dental pulp repair is a difficult clinical problem. In the present study, the authors aimed to mimic the extracellular matrix of dental pulp tissue structurally and compositionally. Nanofibrous silk fibroin (SF) scaffolds containing hydroxyapatite (HAp) nanoparticles were fabricated by using the freeze-drying approach. Rod-shaped HAp was successfully embedded in the composite scaffold, the diameter of which was about 100–200 nm as shown by transmission electron microscopy analysis. The three-dimensional microstructure of the composite scaffold prepared in various ratios of HAp to SF was observed by scanning electron microscopy and the pore size of the optimal scaffold was about 30–120 μm. Meanwhile, the hemocompatibility of the composite scaffolds was evaluated based on their impact on the clotting function by way of activated partial thromboplastin time, prothrombin time and thromboelastographic assays. The scaffolds possessed a low hemolysis rate of red blood cells. Furthermore, cell culture tests using dental pulp stem cells found that the scaffolds had good biocompatibility. There biomimetic HAp/SF composite scaffolds may serve as a promising biomaterial for dental pulp repair.