Conducting polymers are attractive materials in energy storage devices such as supercapacitors and flexible batteries. Among them, polypyrrole (PPy) has been widely studied because of its reversible redox nature, good conductivity, light weight, easy to synthesize, low cost and environmental stability. However, PPy is infusible, insoluble and non-thermoplastics, making it essentially unprocessable. We have recently synthesized a flexible PPy membrane through interfacial polymerization. The aim of this work is to study the effect of glycerine as a plasticizer on the mechanical and electrical properties of the PPy membrane. The polymerization of pyrrole dissolved in chloroform took place at the interface with the aqueous solution containing ferric chloride and methyl orange complex. It was found that glycerine can affect the morphology, pore size distribution, mechanical strength, and the electrochemical behaviors of the PPy membrane. It is likely that glycerine played a key role in the aggregation of PPy nanostructures and could control PPy particle size as well. The electrochemical behavior and charge storage performances of the PPy membrane were also affected by glycerine. To conclude, glycerine may play the role of plasticiser in PPy to improve the mechanical and electrical performance of the PPy membrane.