Sodium zinc phosphate glasses modified by Tl2O addition of composition Na2−xTlxZnP2O7 (x = 0, 0.005, 0.01, and 0.015) are synthesized following the melt quenching technique. The structure of the glass samples is analyzed by the Fourier transform infrared absorption spectroscopy. The results suggest that the phosphate network is polymerized by the addition of Tl+ ions. The electrical conductivity, electric modulus, and dielectric constant characteristics of the glasses are measured over a wide continuous frequency range of 10−2 Hz–1 MHz and in the temperature range 293–473 K by the impedance spectroscopic method. The ac conductivity data are analyzed following the power law exponent (S) and the proposed correlated barrier hopping mechanism (CBH) is the most suitable conduction mechanism in the studied compositions. The electrical modulus formalism is applied to analyze the electric data to study their dielectric relaxation. Non-Debye type relaxation is obtained. From the obtained results, the present glass can be used as a high-energy capacitor.