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In Fuel Cells Technology, the need for lower cost, highly conductive of membrane is crucially demanding. The biopolymers methylcellulose (MC) was chosen as the membrane backbone because of the availability of MC, natural and good barrier against environmental parameters. In order to increase the conductivity value of MC membrane, two experiments were conducted. In experiment 1, different weight of potassium hydroxide (KOH) was added onto MC membrane. For experiment 2, different weight of KOH and polyethylene glycol (PEG) were used in the MC membrane matrix. For both experiments, the membrane was prepared using simple solution casting technique. The conductivity value of MC/KOH and MC/KOH/PEG were investigated by Linear Sweep Voltammetry Potentiostatic (LSV). The findings show that the conductivity value of MC membrane was significantly increased when adding KOH and PEG. For binary solution of MC/KOH, ratio of 75% of MC and 25% of KOH yield the best conductivity 0.78 × 10−5 Scm−1. While for tertiary solution MC/KOH/PEG, the best conductivity value was given by composition of 60/20/20 which is 2.00 × 10−4 Scm−1. The research showed that the addition of KOH or KOH/PEG significantly improved the ionic conductivity of MC membrane. This discovery will play a vital role in the development of low cost, high conductivity in Fuel Cells technology.