The non-linear response of various physical properties of glasses on mixing of alkali ions is a well-known anomaly in materials science. In this paper, the mixed alkali effect in antimony oxide based glasses with composition 60Sb2O3–20WO3–(20 – x)Li2O–x(M2O), where x = 0, 5, 10, 15, 20 (in mol %) and M = Na or K, is studied. The influence of Na/Li and K/Li ratios on ionic AC and DC conductivities is studied. Temperature dependences of the DC conductivity obey Arrhenius-like relation. The conductivity steeply decreases with increasing Na or K content due to larger ionic radius of Na or K ions compared to that of Li. The relation between composition and local movement of electrical charge was investigated and quantified using the measurement of thermally stimulated depolarization currents. The artificial neural network methods for optimizing experimental parameters used in this paper represent a new approach in comparison with works done on glasses with similar composition. The prepared numerical model could be used for the description of the influence of polarization parameters and the optimization of further measurements oriented on activation energies of ion polarization related to local transport of electrical charge, i.e. Li+ and Na+ ions in our case.