Recovering odontoblastic layer and vital pulp tissue are essential but challenging parts in regeneration of the dentin-pulp complex. These two parts have close interactions during dentinogenesis, and thus, angiogenesis is considered to be an integral part of dental pulp regeneration. Regarding previous reports about in vitro effect of prolyl hydroxylase inhibitors on angiogenesis, we investigated the effect of DMOG-embedded poly(ε-caprolactone) fiber (PCLF/DMOG) on odontoblastic differentiation of human dental pulp-derived cells (hDPCs) by transplantation of the dentin slice model. PCLF served as drug-delivering scaffold and cellular niche. hDPCs were seeded onto electrospun PCLF and PCLF/DMOG in dentin slices and then transplanted into nude mice. The surface topography was evaluated for both PCLFs, and DMOG release from the PCLF/DMOG was examined. The effects of the PCLF/DMOG were assessed by histology and RT-qPCR. The PCLF/DMOG treated dentin slices showed higher cellularity with a palisading arrangement of hDPCs and organized collagen fibers. We found that the PCLF/DMOG significantly stimulated the expression of VEGF, DSP, and BSP in the hDPCs (P < 0.05) and mVegfa, mPecam 1, and mNefl in the surrounding host cells (P < 0.05). These results show that PCLF/DMOG has potential in pulp-dentin complex regeneration by promoting odontoblastic differentiation of hDPCs and by enhancing host cell recruitment, angiogenesis, and neurogenesis, through the released DMOG-mediated cell responses.