The primary objective of the investigation was to synthesize biocomposite nanofibres by electrospinning technique with different weight percentages of polycaprolactone (PCL) with chitosan (CS)–pectin (PEC) blend along withthe characterization and antimicrobial activity of the novel electrospun nanofibres. This article for the first time describes the architecture of PCL–CS–PEC electrospun nanofibres along with its antimicrobial activity to the foremost of our information. The present work used CS–PEC, a biocompatible and non-toxic polysaccharide. Electrospinning was used to successfully produce CS–PEC nanofibres coupled with PCL polymer. The structural morphology of the PCL–CS–PEC nanofibres clearly displays the presence of nanofibres. The distinct peaks for the corresponding primary functional groups were clearly identified in the Fourier transform infrared characterization of PCL–CS–PEC nanofibres, as well. TGA confirmed that PCL–CS–PEC nanofibres have greater thermal stability. The antibacterial activity (agar disc diffusion method) of PCL–CS–PEC nanofibres was tested, and it was found to be effective against a wide range of microbial organisms, which aids in wound healing. Nanofibres of 19% PCL–CS–PEC demonstrated better antimicrobial activity against control than 15% and 17%, which might be attributable to concentration. Future studies will be conducted for the validation of the analysed nanofibres using in vivo investigations for the purpose of the wound dressing.