Rapid and complete vascularization of the porous orbital implants after enucleation is vital for reducing postoperative complications, such as exposure and infection. In this study, the porous hydroxyapatite (pHA) scaffolds modified with the mesoporous bioactive glass with and without adding copper (MBG, Cu-MBG) were prepared by sol-gel technique and followed by evaporation induced self-assembly (EISA) process. The macro-/microstructure analysis of the modified scaffolds (i.e., MBG/pHA, Cu-MBG/pHA) showed highly interconnected macropores, and unique mesoporous structures in the pore wall with higher surface area. A primary angiogenic test in a panniculus carnosus muscle model in rabbit indicated that the Cu-MBG coating was significantly beneficial for the vascularization in the porous architecture of the scaffolds in the early stage. These results suggest that the Cu-MBG modification provides a simple and effective strategy to endow favorable biological performances with pHA implants and greater potential for future application in orbit reconstruction.