This investigation demonstrates the electrochemical performance of glass and glass–ceramic NaMn_1−x(VO)_xPO₄ (x = 0.1, 0.3, 05, 0.7 mol%, and labeled as NM_1−xV_xP) cathode material system via phase details, structural illustration, electronic conductivity, and reversible capacity, etc. Pro‐crystal calculation analysis is used to monitor Na⁺ ion pathways’ migration for as‐precipitated NaMnPO₄, Na₂MnP₂O₇, and NaVO₃ phases. The highest conductivity is achieved (≈5.92 × 10⁻⁷ S cm⁻¹) for the glass–ceramic sample having x = 0.3 mol% (NM_0.7V_0.3P) due to the lowest charge transfer resistance (R_ct). Electrochemical measurements of the best conducting sample using coin half‐cell exhibit two distinct voltage plateaus at 2 and 2.9 V versus Na/Na⁺, facilitating the active centers in two directions. The cyclability test of best‐conducting NM_0.7V_0.3P glass–ceramic network exhibits adequate reversible capacity up to 97% of the specific capacity even up to 50 cycles, which satisfies its superior stability for longer durations.