We develop a Magnetic Cluster Expansion (MCE) model for binary bcc and fcc Fe–Cr alloys, as well as for fcc Fe-Ni alloys, and apply it to the investigation of magnetic properties of these alloys over a broad interval of concentrations, and over a broad interval of temperatures extending well over 1000 K. We show how an MCE-based Monte Carlo study describes the magnetic properties of these alloys, for example the composition and microstructure dependence of the Curie temperature, the non-collinearity of magnetic structures found in bcc Fe-Cr alloys, phase transitions between bcc and fcc in Fe-Cr, and the enthalpy of mixing of Fe-Ni alloys. The results of simulations are in excellent agreement with experimental observations.