The present work deals with the reinforcement and the resulting property enhancement of polyindole (PIN)/poly(vinyl alcohol) (PVA) blend using zinc ferrite (ZnFe2O4) nanoparticles. The polymer blend nanocomposite samples have been prepared using a simple in situ polymerization method. The structural changes in the polymer blend resulting from its interaction with ZnFe2O4 have been identified by Fourier transform infrared (FTIR) spectroscopy and X‐ray diffraction (XRD) studies. The FTIR spectra of blend nanocomposite showed the presence of ZnFe2O4 nanoparticles at 580 cm−1. The chemical interactions between the polymer and ZnFe2O4 have been confirmed by the shift in the position of FTIR peaks. The XRD results indicate the increase in the crystalline nature of the polymer blend with the incorporation of ZnFe2O4 nanoparticles into the blend. Scanning electron microscopy photographs of the nanocomposites show the dispersion of nanoparticles in PIN/PVA blend, while transmission electron microscopy images reveal the presence of spherically shaped nanoparticles in the polymer blend with an average size of 15 nm. The glass transition temperature of polymer blend composite has been shifted to a higher value, and thermal stability of the polymer blend improved with the addition of ZnFe2O4 nanoparticles. The incorporation of ZnFe2O4 nanoparticles in the PIN/PVA blend matrix leads to a significant improvement in overall mechanical properties, AC and DC conductivity. The dielectric properties are found to be higher for ZnFe2O4‐reinforced blend systems than the pure blend system due to polarization exerted by the incorporation of nanoparticles.