Hydroxymetal-clay complexes, which contain reactive surface hydroxyl groups, have a strong affinity for both heavy-metal cations and oxyanions and hence can serve as efficient sorbents for ionic contaminants. The co-sorptive behavior of heavy-metal cations and oxyanions on the surface of hydroxymetal-clay complexes is not well understood, however. The objective of the present investigation was to help bridge that gap by determining the feasibility of co-sorbing Cd cations and phosphate from aqueous solution to a hydroxyiron-montmorillonite complex (HyFe-mont). A montmorillonite-rich clay from Inner Mongolia, China, was the starting material. The results showed that Cd and phosphate could be sorbed, simultaneously and synergistically, to HyFe-mont without a change in solution pH. Similarly, when phosphate was sorbed before Cd, the sorption capacities were comparable to those obtained in the simultaneous sorption experiment, and the solution pH did not change. When Cd was pre-sorbed, however, the subsequent sorption of both Cd and phosphate decreased as did solution pH. X-ray photoelectron spectroscopy (XPS) indicated that the binding energies of P2p, Cd3/2, and Cd5/2 were of similar magnitude for both the simultaneous sorption system and the phosphate pre-sorbed system. In addition, the single Cd and Cd pre-sorbed systems had similar Cd3/2 and Cd5/2 binding energies. The combined sorption and XPS results suggested that sorbed phosphate and Cd formed P-bridged ternary complexes on the HyFe-mont surface, contributing to the synergistic uptake of the contaminants in the simultaneous sorption system.