Currently, Selective Laser Melted (SLM) titanium alloys can meet the demands of personalized medical devices, but their poor surface roughness results in suboptimal surface biocompatibility. A low cost, high-efficiency 3D printing method, binder jetting additive manufacturing (BJAM), effectively address this issue. Furthermore, the application of bioactive coating on the BJAM-ed titanium alloy implants can enhance their surface bioinertness. This study synthesized Mn-MOFs via a solvothermal method, and then investigated the effects of synthesis temperature on the morphology, structure, and cyto-toxicity of Mn-BTC. Finally, the Mn-BTC with the best biocompatibility were coated on the BJAM-ed TC4 implant. The results indicate that Mn3+ was gradually reduced to Mn2+ by the thermodynamic driving forces, prompting a morphological transition of Mn-BTC from asymmetric polyhedrons to uniform spheres. This valence-morphology synergy significantly reduces the cytotoxicity of Mn-BTC synthesized at 170 degrees C. Subsequently, the 170 degrees C-synthesized Mn-BTC was coated on the BJAM-TC4 titanium alloy implants via micro-arc oxidation (MAO) to fabricate a Mn-BTC/MAO-TC4 coating. This coating not only effectively improves the RGR (increase by 12.1 %) compared to BJAM-TC4 but also significantly promotes BMSC adhesion performance. This study unveils the structure-activity relationship between temperature and morphology in Mn-BTC, providing a novel strategy for the surface functionalization of BJAM titanium alloy implants.