The essential part of electrochemical devices, such as fuel cells and batteries, is the polymer electrolyte with good mechanical, thermal, and chemical stability. The search for a new proton-conducting membrane with easy processability, non-toxic, and low-cost has been growing rapidly. The bio-based polymer electrolytes are now receiving much attention due to the green environment. Among the commercially available biopolymers, iota-Carrageenan (I-Carrageenan) is one of the biopolymer with good film-forming nature and with good mechanical stability. I-Carrageenan-based biopolymer membranes doped with ammonium bromide (NH4Br) have been prepared using solution-casting technique, and distilled water is used as a solvent. The prepared I-Carrageenan-based biopolymer membranes have been characterized using FTIR, XRD, and AC impedance techniques. The complexation between the polymer and salt has been revealed by FTIR. The increase in the amorphous nature of the film due to the addition of salt has been confirmed by XRD. From AC impedance technique, the conductivity of pure I-Carrageenan has been found to be 1.46 × 10−5 S/cm. The addition of different wt% of NH4Br increases the conductivity and reaches the highest value of 1.08 × 10−3 S/cm for 20% NH4Br, and the conductivity decreases on further addition of NH4Br due to the formation of ion aggregates. © 2016, Springer-Verlag Berlin Heidelberg.