This study explored a novel modification method for porous polyetheretherketone (PEEK) implants using a biomimetic coating to achieve synergistic enhancement of vascularization and bone regeneration. Inspired by the natural extracellular matrix (ECM) structure (consists of growth factors and matrix proteins), a biomimetic dual-factor coating capable of releasing bone morphogenetic protein-2 (BMP-2) and fibronectin (FN) was coated on the surface of 3D-printed porous PEEK scaffolds using polydopamine (PDA) as a binder. Experiments conducted with MC3T3-E1 cells or HUVECs in co-culture with scaffolds revealed that the biomimetic coating not only synergically promoted cell migration, adhesion and proliferation, but also enhanced angiogenesis and osteogenic differentiation simultaneously in vivo. The synergistic effect is attributed to the crosstalks between intracellular signaling pathways of FN and BMP-2, as well as the sustained release on account of their combination mitigates explosive release and degradation of BMP-2. Overall, this study designed a novel biomimetic coating modified PEEK scaffolds and confirmed the synergistic mechanism of the scaffolds on osteogenic differentiation and angiogenesis for the first time. These insights have significant implications for the clinical transformation of PEEK dental implants.