In the presented paper solid solutions of complex Nb oxide systems (1-x) NaNbO3 - xCa(2)Nb(2)O(7) and (1-x) NaNbO3 - xSr(2)Nb(2)O(7) were produced using two-stage solid-phase synthesis with the following sintering by means of the regular ceramics technology; their dissipative characteristics were studied in the frequency range of (1.0 divided by 11.0) GHz. It was demonstrated that the maximum values of microwave power absorption in systems of solid solutions, which contain phase transitions of various nature, are observed, generally, at phase boundaries. The paper suggests that, presumably, that phenomenon is related to the development of defect situation in corresponding media due to opening of chemical bonds during rearrangement of structure, accumulation of vacations and impurity phases and increase of number of interphase boundaries. The study revealed the features of dielectric properties of the discussed solid solutions. It was concluded that it is possible to use the obtained results for the development of new functional materials, which can be applied in various branches of industry using microwave technologies, in particular, for solution of problems of electromagnetic compatibility of radioelectronic systems, as well as for development of components of electronic devices, including IC technology.