Coagulation is a widely applied and important process for water treatment, and the development of improved coagulation reagents continues to be a practical objective. However, mechanisms guiding the development of composite coagulants remain insufficiently understood. In addressing this deficiency, this study has investigated the enhancement of conventional Fe(III) coagulation by composite coagulants that incorporate an additional metal salt (Me: Ca²⁺, Al³⁺, Ti⁴⁺, Zr⁴⁺), focusing on the mechanistic roles that Me constituents play in Fe-based coagulation. The effectiveness of composite coagulants was assessed through floc size and the removal of organics and phosphates. Results demonstrated that Me constituents enhance coagulation performances to varying extents, with Al³⁺ and Zr⁴⁺ showing the most significant improvements. FT-ICR MS analysis at the molecular scale reveals that additional Me facilitates the removal of humic acid, hydrophobic macromolecules, and highly aromatic organics containing polycarboxyl and secondary carbon structures. EXAFS results indicate that co-hydrolysis of Fe³⁺ with Me disrupts the formation of conventional ferrihydrite at the nanoscale of flocs and promotes the development of Fe-phosphate clusters. Me effectively reduces the corner- and edge-sharing coordination between FeO₆ octahedra within clusters, resulting in a more dispersed arrangement of FeO₆ polymers with available binding sites for the PO4 tetrahedron. The shortened Fe-P bond indicates that Me promotes a more compact link between FeO₆ octahedra and PO₄ tetrahedra. By revealing how cations in composite coagulants change the nanoscale structure of Fe flocs to affect macroscopic coagulation, this study enhances the understanding of metal ion interactions during co-hydrolysis and co-precipitation in natural systems.