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This paper deals with development and characterization of the solid biopolymer electrolyte using Sodium alginate as the host biopolymer and magnesium perchlorate used as a doping salt. Membranes are prepared via solution casting technique. Several characterization techniques, such as X-ray and diffraction, Fourier transform infrared spectroscopy, differential scanning calorimetry, AC impedance spectroscopy, linear sweep voltammetry, and transference number measurement are performed to characterize the prepared biopolymer membrane. The highest ionic conductivity 2.41 × 10 −3 S cm −1 is observed for prepared solid biopolymer electrolyte contains 40:60 m wt% of NaAlg:Mg(ClO 4 ) 2 . The electrochemical stability of highest ion conducting biopolymer membrane is observed at 3.62 V. A primary magnesium battery is constructed using the highest ionic conducting biopolymer membrane and the open circuit voltage of the fabricated magnesium battery is found to be 2.0 V.