Polymer membranes of ferrites nanoparticles, glycerol, and poly(vinyl alcohol) (PVA) were fabricated using a solution casting method. Spinel ferrites nanoparticles, CuFe2O4 or ZnFe2O4, and glycerol were used as dopants to control the membranes' electrical conductivity. The morphology, composition, and interaction between PVA and the dopants were investigated byscanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), differentialscanning calorimeter (DSC), and thermal gravimetric analysis (TGA). Electrical characterization of the membranes was conducted by impedance spectroscopy using frequencies between 1 and 106 Hz and variable temperatures. The results revealed a negative temperature coefficient of the resistance of the membranes. Additionally, membranes with ZnFe2O4 nanoparticles exhibit higher electrical impedance than those with CuFe2O4 nanoparticles. Therefore, electrical conductivity could be controlled using a suitable dopant's composition and concentration. The membranes presented in this study exhibit semiconducting properties, thus, they have potentials to be utilized in multiple applications including the flexible organic‐based device. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48821.