To meet requirements of regenerative medicine, novel biomaterials should either mimic natural tissues or enable multi‐way stimulation of cells. In this study, we prepared two types of hybrids, differing in composition and morphology by decorating CNTs with iron oxide nanoparticles (IONs), and introduced them into the poly(ε‐caprolactone) (PCL) to prepare biocompatible composite films using casting method. The effect of the type of multi‐walled carbon nanotube (MWCNT)/ION hybrid and its content on the composites’ parameters that are important for cell‐biomaterial interaction that is, surface morphology, wettability, surface energy, and mechanical properties, was examined and compared with results obtained for the PCL, PCL/MWCNT and PCL/ION films. Additionally, materials with IONs were characterized in terms of their magnetic properties. Irrespective of the nanoaddition type, CNT‐based films with content of CNTs up to 1 wt% were characterized by similar surface parameters (completely distinguishable from the PCL film). Pristine CNTs were found to improve the tensile strength of the PCL films while IONs caused its reduction. Interestingly, composites containing 1 wt% of the hybrid, with a 1:1 ratio of MWCNTs and IONs, exhibited tensile strength similar to the PCL/CNTs film. Decoration of CNTs with IONs was found to significantly improve the dispersion level of magnetic phase within the polymer. POLYM. COMPOS., 40:E1818–E1830, 2019. © 2018 Society of Plastics Engineers