The structural and electrical characteristics of (Mg,Zn)O ceramics produced using the solid state reaction at 1100 °C for 3 hours were studied applying X-ray diffraction and IR reflection spectroscopy as well as means of direct current measurements versus MgO content in initial charge (varied from 0 to 100 mol.%). It has been shown that electrical conductivity extracted from the IR reflection spectra corresponds to that of hexagonal phase in a solid solution, while plasmon in cubic phase was not observed. The electron concentration in the hexagonal grains of solid solution prepared with MgO content below 30 mol. % in the charge was found to be close to that of ZnO grains. It shows the tendency to decrease with further growth of the MgO content, which was explained by extraction of zinc interstitials, responsible for ZnO conductivity, from ZnO under formation of the MgZnO cubic phase. The direct current measurements have shown the lower conductivity as compared to the value estimated from IR reflection spectra. This fact along with the superlinearity of current-voltage characteristics has been explained by the presence of intergranular barriers, which does not allow obtaining information on the concentration of free electrons in the grain by this method. The possible nature of intergranular barriers as well as the role of grain boundaries in the DC conductivity of samples has been discussed.