Abstract This work provides a convenient strategy for preparation of conducting polycaprolactone (PCL)/polyaniline (PAni) nanofibers, useful for development of optoelectronic sensors and devices. PCL/PAni nanofibers were obtained by electrospinning technique and characterized by SEM, FTIR, thermal analysis, and DC electrical conductivity. The influence of the experimental conditions in the electrospinning process, such as the applied voltage, on the nanofiber morphology was discussed in detail. Incorporation of PAni into PCL nanofibers significantly increased the electrical conductivity from a non-detectable level for the neat PCL to 0.032 ± 0.022 S/cm for the nanofibers containing 7.5 wt.% PAni. Therefore, electrospun PCL/PAni nanofiber mats presented optical and electrical properties, that awaken the possibility of applications for these materials as acid-base sensors and electrochromic devices.