Conductive polymers can stimulate the adhesion and proliferation of several cell types being an interesting material to be applied in the field of tissue engineering. In this application, the addition of a thermosensitive polymer has been pointed out as an attractive strategy to improve mechanical strength and to provide conformation changes at temperature close to human body temperature. The main goal of this work was to evaluate the physical–chemical properties and promotion of cell proliferation and possible application as scaffolds for tissue engineering of blends of poly(N‐vinylcaprolactam) (PNVCL) and poly(N‐vinylcaprolactam‐co‐butylacrylate) (PNVCL‐co‐ABu) with poly(3‐hexylthiophene) (P3HT). Both polymers were synthesized and their chemical structures were confirmed by Fourier Transform Infrared (FT‐IR) and nuclear magnetic resonance (NMR) analyses. The materials were processed in films form for structural characterization, impedance measurements, and thermogravimetric analysis. The in vitro biological assays were performed using the materials as electrospun mats. The FT‐IR was also used to characterize the blends. The addition of P3HT did not change thermal stability and showed low conductivity values of the blends. Comparing the in vitro behavior of the blends and the polymers it was possible to conclude that the presence of P3HT improved cytocompatibility and promoted cell proliferation.