In the present work, polypyrrole hollow fibers (PPy-HFs) were fabricated by sacrificial removal of soft templates of electrospun polycaprolactone (PCL) fibers with polypyrrole (PPy) coating through chemical polymerization of pyrrole monomer. Different physicochemical properties of as-fabricated PPy-HFs were then studied by Field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), Fourier transform infra-red (FT-IR) spectroscopy, Differential scanning calorimetry/Thermogravimetric analysis (DSC/TGA), and X-ray photoelectron spectroscopy (XPS). The photothermal activity of PPy-HF was studied by irradiating 808-nm near infra-red (NIR) light under different power values with various concentrations of PPy-HFs dispersed in phosphate buffer solution (PBS, pH 7.4). These PPy-HFs exhibited enhanced photothermal performance compared with polypyrrole nanoparticles (PPy-NPs). Furthermore, these PPy-HFs showed photothermal effect that was laser-power- and concentration-dependent. The photothermal toxicity of the resulting nanofiber was evaluated using cell counting kit-8 (CCK-8) and live and dead cell assays. Results showed that these PPy-HFs were more effective in killing cancer cells under NIR irradiation. In contrast, hollow-fiber showed no cytotoxicity without NIR exposure. Among different nanofiber formulations, PPy-160 exhibited the highest photothermal toxicity. It could be explained by its enhanced photothermal performance compared to other specimens. The resulting PPy-HFs showed superior drug loading capacity to PPy-NPs. This might be attributed to adequate binding of the drug into both luminal and abluminal hollow-fiber surfaces. Fabrication of this substrate type opens a promising new avenue for architectural design of biocompatible organic polymer for biomedical field. (C) 2018 Elsevier Inc. All rights reserved.