The potential of next‐generation batteries lies in solid biodegradable polymer electrolytes. This research delves into a solid blend polymer electrolyte (SBPE) for magnesium conduction, utilizing a chitosan‐dextran blend matrix doped with magnesium perchlorate (Mg(ClO4)2) salt. The electrolyte films are prepared using a conventional solution casting technique. Through techniques like X‐ray diffraction and Fourier transform infrared spectroscopy, the successful incorporation of Mg(ClO4)2 into the blend matrix is confirmed. Notably, the SBPE containing 30 wt% of Mg(ClO4)2 demonstrates the highest ionic conductivity of 6.99 × 10−4 S cm−1 and a prominent ionic transference number of 0.84. Thermogravimetric analysis is carried out to study thermal stability. Differential scanning calorimetry analysis of the electrolyte systems gives insight into their thermal properties. Additionally, it showcases favorable electrochemical stability of 2.66 V. The oxidation and reduction peaks are observed in the cyclic voltammetry curve of the highest conducting sample. Furthermore, the discharge performance of Mg/(CS + DN + Mg(ClO4)2)/cathode cells is explored with varied cathode materials, illustrating the SBPE's potential for magnesium‐ion batteries. This study unveils a sustainable, biodegradable, and economical electrolyte solution for advanced energy storage systems.