Results of studies of the structure, microstructure, dielectric characteristics and the Mössbauer effect of solid solutions of the (1-x)PbFe1/2Nb1/2O3 - xPbFe2/3W1/3O3 system in wide temperature range are presented. X-Ray diffraction and Mössbauer spectra showed that in the PbFe1/2Nb1/2O3 there are regions with a high and low concentration of Fe3+ ions - clustering; in PbFe2/3W1/3O3 there is a process of local ordering of cations in the B-sublattice. The number of local states of Fe3+ ions indicates the occurrence of partial ordering of ions in the B-position in the system (1-x)PbFe1/2Nb1/2O3 - xPbFe2/3W1/3O3. As x concentration increases, a nearly linear increase in the N é el temperature was observed. Investigation of ceramic cleavage surfaces allows us to conclude that the grain structure and the dependence of the grain size on the amount of the PbFe2/3W1/3O3 are inhomogeneous. It is shown that additional maxima in the dependence of the imaginary part of relative complex permittivity appearing above the phase transition temperature are associated with the onset of hopping conduction. •The solid solutions of the (1-x)PbFe1/2Nb1/2O3 - xPbFe2/3W1/3O3 system were produced.•The partial ordering of ions Fe3+ in the B-position in the system (1-x)PbFe1/2Nb1/2O3 - xPbFe2/3W1/3O3 was found.•The dependence of the grain size on the amount of the PbFe2/3W1/3O3 was demonstrated.•The hopping conduction in the solid solutions of the (1-x)PbFe1/2Nb1/2O3 - xPbFe2/3W1/3O3 system was found at analysis of the permittivity.