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Polymer nanocomposites films, based on sodium alginate (NaAlg) and polyvinyl alcohol (PVA) complexed with zinc oxide nanoparticles (ZnO NPs) and iron oxide nanorods (Fe3O4 NRs) as nanofiller, were prepared by solution casting technique. Different techniques were used to describe the prepared films. XRD and FTIR were used to pinpoint the complexation of the nanofiller with the polymer mixture. The XRD investigation verified the existence of the crystalline peaks of ZnO/Fe3O4 NPs in the polymeric matrices. The average particle size of nanocomposite was 23 nm. TEM image of the ZnO nanopowder confirming the spherical form of nanoparticles with average size 30 nm. The TEM image of Fe3O4 NRs reveals the free nanorods are around 9–23 nm in diameter and 130–350 nm in length. Peak positions and intensity variations in the FTIR absorption spectra are observed when the concentration increases from 2 to 8 wt% of ZnO NPs/Fe3O4 NRs. AC conductivity showed that the NaAlg/PVA‐(8 wt%) ZnO/Fe3O4 NPs nanocomposites have higher electrical conductivity than NaAlg/PVA blend. For samples of 8% ZnO/Fe3O4, the σdc of nanocomposites reached 3.66 × 10−8 S cm−1. ZnO/Fe3O4 nanoparticles considerably improved the nanocomposites' ability to conduct electricity. For the development of functional composite materials for the manufacture of electrical devices, sensors, and high‐energy storage capacitors, the enhanced characteristics of synthesized NaAlg/PVA‐ZnO/Fe3O4 nanocomposites can be helpful. [ABSTRACT FROM AUTHOR]