Polyetheretherketone (PEEK) implants have emerged as a clinically favored alternative to titanium alloy implants for cranial bone substitutes due to their excellent mechanical properties and biocompatibility. However, the biological inertness of PEEK has hindered its clinical application. To address this issue, we developed a dual-functional surface modification method aimed at enhancing both osteogenesis and antibacterial activity, which was achieved through the sustained release of chondroitin sulfate (CS) and levofloxacin (LVFX) from a biomimetic polydopamine (PDA) coating on the PEEK surface. CS was introduced to promote cell adhesion and osteogenic differentiation. Meanwhile, incorporation of antibiotic LVFX was essential to prevent infections, which are a critical concern in bone defect repairing. To our delight, experiment results demonstrated that the SPKD/CS-LVFX specimen exhibited enhanced hydrophilicity and sustained drug release profiles. Furthermore, in vitro experiments showed that cell growth and adhesion, cell viability, and osteogenic differentiation of mouse calvaria-derived osteoblast precursor (MC3T3-E1) cells were significantly improved on the SPKD/CS-LVFX coating. Antibacterial assays also confirmed that the SPKD/CS-LVFX specimen effectively inhibited the growth of Escherichia coli and Staphylococcus aureus, attributable to the antibiotic LVFX released from the PDA coating. To sum up, this dual-functional PEEK implant showed a promising potential for clinical application in bone defects repairing, providing excellent osteogenic and antibacterial properties through a synergistic approach.