Solution combustion technique is used for synthesizing La2−xSrxMo1.95V0.05O9−δ (x = 0–0.14). The properties of these compounds are investigated via X‐ray diffraction (XRD), scanning electron microscopy, differential scanning calorimetry (DSC), and electrochemical impedance spectroscopy. No secondary phases are detected in XRD. Complete suppression of αβ phase transition is evident via RT‐XRD and DSC in all doped compounds. Throughout the temperature regime, conductivity is enhanced compared with parent La2Mo2O9. The conductivity plot reveals an Arrhenius to Vogel–Tammann–Fulcher (VTF) type of temperature‐dependent conduction behavior.