This study investigates anodic surface modification of the Ti₄₇Cu₃₈Zr_7.5Fe_2.5Sn₂Si₁Ag₂ bulk metallic glass in a nontoxic potassium pyrophosphate electrolyte and its impact on corrosion behavior and cytocompatibility. The treatment forms bilayered oxide films (20–90 nm) via selective Cu dealloying and Ti/Zr oxide formation. Analyses by transmission electron microscopy and glow discharge optical emission spectroscopy reveal a dense inner amorphous layer and a porous outer layer containing metallic Cu nanocrystals, formed through Cu mobilization and reduction. Electrochemical testing demonstrates that anodization at 1.3 V vs. saturated mercury sulfate electrode significantly enhances corrosion resistance in chloride-containing phosphate-buffered saline and reduces Cu ion release by approximately 50% compared to the untreated state. Contact angle measurements confirm increased surface hydrophilicity due to the Ti/Zr oxide matrix. Biological evaluation shows that this optimized surface promotes human bone marrow stromal cell spreading and focal adhesion formation. It results in a 4.5-fold increase in cell proliferation and elevated activity of the osteogenic marker tissue nonspecific alkaline phosphatase, indicating enhanced osteogenic differentiation. These findings highlight that controlled anodization in a nontoxic pyrophosphate electrolyte can tailor surface oxide structure and composition, simultaneously improving corrosion resistance, cytocompatibility of Ti–Cu-based metallic glasses for advanced biomedical implants.