Display omitted ► The synthesized PPCA coated Fe3O4 NPs might be applied magnetic heterogeneous catalyst. ► Superparamagnetic Fe3O4–PPCA NPs were fabricated by reflux route for the first time in this study. ► The product has potential applications in nanoelectronics and biomedical devices. Piperidine-4-carboxylic acid (PPCA) functionalized Fe3O4 nanoparticles as a novel organic–inorganic hybrid was fabricated and characterized by XRD, FT-IR, VSM, and TEM techniques. Its detailed electrical properties are also presented. Composition was determined as Fe3O4, while particles were observed to have spherical morphology. VSM measurement proved the super-paramagnetic property of the as synthesized nanocomposite. ac and dc conductivity measurements indicated semiconductor characteristics and changing trends with temperature because of reorganization of the nanocomposite. dc conductivity is strongly temperature dependent and is classified into three regions. Analysis of the real and imaginary parts of the permittivity of nanocomposite showed the ionic polarization mechanism consisting of ionic conductivity and interfacial polarization.