In this study, the nature of the electrical transport and structural changes resulting from the systematic substitution of Al₂O₃ with K₂O in 40P₂O₅-(25−x)Al₂O₃-35Na₂O-xK₂O, where x = 5.0, 7.5, 10.0, 12.5, and 15.0 mol% (PANxK), is investigated. The impact of the changes in glass structure and its correlation to electrical properties is presented. The mixed alkali effect (MAE) is observed due to the presence of two different alkali oxides, resulting in a non-monotonic trend in the studied glass properties. The infrared spectra show the shift and diminishing of the bands related to the P–O–P/P–O–Al bridges with increasing K₂O content and changes in bands related to depolymerization of the glass network, which is confirmed by the trend of the Tg values. The minimum value of DC conductivity is obtained for glass with x = 12.5 mol%. With the overall increase in alkali content, the number of non-bridging oxygens increases, also affecting the conductivity values. Frequency-dependent conductivity spectra analyzed by Summerfield, Baranovskii-Cordes and Sidebottom scaling procedures revealed interesting features and signature of the MAE in the short-range dynamics of the potassium and sodium ions, both for individual glass composition and glass series as a whole. This study showed the impact of MAE and local glass structure on the electrical features and the prevailing of one effect over the other as a function of the glass composition. MAE dominates in a wider range, but with the significant increase in alkali content, MAE is consequently overpowered.