In this paper, we present the method for determination of effective electromagnetic parameters of complex building materials. By application of the proposed algorithm, it is possible to analyze electromagnetic field distribution for large-scale problems with heterogeneous materials. The two-dimensional numerical model of building components (hollow brick) with periodic boundary conditions was solved using the finite-difference time-domain method (FDTD) and discussed. On this basis, the resultant transmission coefficient was found and then the equivalent relative permeability and electric conductivity of heterogeneous dielectric structures, in the developed homogenization algorithm, were identified. The homogenization of material properties was achieved by performing a multi-variant optimization scheme and finally, selecting optimal electric parameters. Despite the analysis of heterogeneous building materials, the presented algorithm is shown as a tool for the homogenization of complex structures when scattering of a high-frequency electromagnetic field is considered.