A relation of transport properties of polymerized electrolytes to their structure is considered. A kinetics of electrode processes, occurring at the boundary of Ni electrodes - K2O · B2O3 · SiO2 melt with additive of NiO, is studied over the temperature range of 973-1153 K. The diffusion coefficient of Ni2+ ions and resistivity of electrolyte (0.25-3% NiO) are measured by using infrasound frequencies of alternating current. The complicated character of dependences of Ni ions diffusion coefficients and liquid borosilicate resistivity on composition testifies the essential structural variations in melt on NiO addition.