In this study, a single step method for large scale fabrication of hollow microspheres with a narrow size distribution is presented. PolyBenzoThiadiazole (PolyBT), a conducting polymer, was electrosprayed at high voltage to obtain microspheres. Hollow spheres of size ranging from 4.1 to 7.3 m were observed through scanning electron microscope images, without any chemical degradation as shown by FTIR studies. In addition, these microspheres demonstrated a change in optical and hydrophobic properties as exhibited by the UV-visible and contact angle measurements. Thus providing interesting opportunities for use in biomedical applications, sensors as well as optoelectronic devices.