FGM thermodynamics has been mostly based on adaptation of classical Gibbs-Helmholtz approach for infinite systems to locally “homogeneous” zones. A statistical sum calculation in this theory cannot predict inhomogeneous distributions. A new approach to the statistical description of solid solutions is suggested, which takes into account possible formation of spatially inhomogeneous simultaneous particle and field distributions in finite space domains. The formation of new periodical or gradated structure in binary system is described. The effective free energy of system was determined and the condition of formation of such spatially inhomogeneous distribution of interacting particles was obtained. New method may be applied to FGM to calculate ab initio free energy of these systems without usual limitations of classical theory.