In composite structures or complex concrete members, some concrete bears multiple forces, called core concrete. The properties of the core concrete are variable under complex stress conditions, which will influence the structure performance analysis. Therefore, it is necessary to establish an accurate and theoretical constitutive model of concrete under complex stress conditions. The elastic–plastic properties of concrete in complex stress conditions were analyzed first. Then, the failure criterion of concrete in complex stress conditions was discussed to identify the key parameters. And the relationship between the stress–strain curve and failure criterion was analyzed through mathematical derivation. Finally, the multi-dimensional iterative constitutive model of concrete under complex stress conditions was established and verified. Based on the analysis results, the concrete under multi-axial stress conditions shows a spindle-shape stress envelope diagram. The failure criterion should be established by the analysis of concrete under high multi-axial compression conditions, tension–compression conditions, and shear–compression conditions. The plastic modulus is the key to reflecting the plastic strain development trend and the stress–strain relationship.