A magnetic polymer hybrid film (MPHF) with a thickness of ~80 μm, composed of iron oxide nanoparticles (IONPs) in a polystyrene (PS) matrix, was successfully prepared. Its structure and morphology were analyzed by HRTEM, XRD, and FTIR. The optical and magnetic behaviors were studied by UV–Vis spectroscopy and VSM, respectively. The main relaxation of the MPHF was characterized by dynamic mechanical analysis (DMA), and the molecular mobility was analyzed by a fractional Zener model (FZM). Results obtained by DMA reveal the mechanical manifestation of the
α‐relaxation for both, PS and MPHF, and how this process is modified by IONPs into MPHFs. Good agreement between experimental DMA spectra and the theoretical results calculated from the FZM was obtained. Fractional parameters
a and
b characterize the molecular mobility at low and high temperatures, respectively. These results show that at low temperatures (
a parameter), molecular mobility is slightly affected by the presence of IONPs, while at high temperatures (
b parameter), molecular mobility is affected in a greater degree. IONPs decrease the molecular mobility of PS matrix; this effect is more pronounced at temperatures above the glass transition temperature. These results validate the effect of IONPs on PS matrix considering future applications of the MPHFs. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47840.