A direct borohydride fuel cell (DBFC) employing a poly (vinyl alcohol) hydrogel membrane electrolyte (PHME) is reported. The DBFC employs an AB₅ Misch metal alloy as anode and a goldplated stainless steel mesh as cathode in conjunction with aqueous alkaline solution of sodium borohydride as fuel and aqueous acidified solution of hydrogen peroxide as oxidant. Room temperature performances of the PHME-based DBFC in respect of peak power outputs; ex-situ cross-over of oxidant, fuel, anolyte and catholyte across the membrane electrolytes; utilization efficiencies of fuel and oxidant, as also cell performance durability are compared with a similar DBFC employing a Nafion®-117 membrane electrolyte (NME). Peak power densities of ∼30 and ∼40 mW cm^-2 are observed for the DBFCs with PHME and NME, respectively. The crossover of NaBH₄ across both the membranes has been found to be very low. The utilization efficiencies of NaBH₄ and H₂O₂ are found to be ∼24 and ∼59%, respectively for the PHME-based DBFC; ∼18 and ∼62%, respectively for the NME-based DBFC. The PHME and NME-based DBFCs exhibit operational cell potentials of ∼ 1.2 and ∼ 1.4 V, respectively at a load current density of 10 mA cm^-2 for ∼100 h.