In this work, a polycaprolactone (PCL) electrospun mat was prepared by the electrospinning method, and polypyrrole (PPy) was coated by in situ chemical polymerization in the presence of phytic acid (PA). Significant PPy coating over the electrospun mat was observed when polymerization was mediated with PA. Different physicochemical characterizations were performed. The thickness and weight of the composite mat were found to increase as a function of increasing PA content during polymerization compared to those in the absence of phytic acid. PA increased the degree of pyrrole polymerization and subsequent crosslinking, which reduced the resistivity of the composite material. It is proposed that PA enhanced the chemical polymerization of pyrrole by binding pyrrole radical cations followed by subsequent polymerization. Overall, this method of PPy-PCL composite mat production seems to be highly beneficial for large-scale production with improved conductivity at an economically cheap rate.