AbstractThe objective of this work was to fabricate nanofibres composed of polycaprolactone (PCL) and κ‐carrageenan (kC) by employing an anionic surfactant, sodium bis(2‐ethylhexyl) sulfosuccinate (AOT). This study examined the role of the surfactant in PCL/kC/AOT (hybrid) nanofibre preparation using SEM, AFM, Fourier transform infrared spectroscopy, XRD and DSC. The wettability and water uptake percentage of the nanofibres were investigated. An antimicrobial study was conducted against bacterial strains using a colony‐counting assay, and changes in bacterial morphology were monitored using TEM. The results demonstrated that the hybrid nanofibres had a uniform and smooth structure, which might be attributed to the improved compatibility between polymers in the presence of the surfactant. The incorporation of AOT in the matrix resulted in a reduction in the mean fibre diameter and surface roughness. The hybrid nanofibres increased water absorbency is evidence of their high hydrophilicity, which can be explained by the simultaneous impact of kC and AOT. The hybrid nanofibres exhibited effective activity against Staphylococcus aureus and Escherichia coli. © 2024 Society of Chemical Industry.