We have developed an ab initio method for calculating the static correlation functions in substitutional alloys, which, for example, describes their atomic short-range order (ASRO) as given by atomic diffuse scattering intensities. For magnetic alloys, a contribution to the total diffuse scattering intensities also results from the moment-chemical correlations (i.e., variations of local moments due to changes in the chemical environment). The response functions, which may be directly compared to single crystal neutron-scattering, are derived from a mean-field statistical mechanical description of compositional fluctuations in alloys. The statistical averages are performed via the Korringa–Kohn–Rostoker coherent-potential approximation, which incorporates the electronic structure of the high-temperature, chemically disordered state. For magnetic Fe-13.5% V alloys, we present results of first-principles calculations of the ASRO, which compare very well with the (quenched) single crystal data obtained by Cable et al.,1 and predict the structure of the moment-chemical correlations. Moreover, we determine the origin of the q-dependent structure in these correlations. In the future, this will allow direct comparison of neutron data with theory to understand more fully the underlying mechanisms which drive, e.g., ASRO.