In this article, we report the electrochemical synthesis and simultaneous in situ coating of magnetic iron oxide nanoparticles (MNPs) with polyvinylpyrrolidone (PVP) and polyethylenimine (PEI). The cathodic deposition was carried out through electro-generation of OH− on the surface of cathode. An aqueous solution of Fe(NO3)3·9H2O (3.4 g/L) and FeCl2·4H2O (1.6 g/L) was used as the deposition bath. The electrochemical precipitation experiments were performed in the direct current mode under a 10 mA cm−2 current density for 30 min. Polymer coating was performed in an identical deposition bath containing of 0.5 g PVP and 0.5 g PEI. The deposited uncoated and PVP-PEI coated MNPs were characterized through powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), dynamic light scattering (DLS), vibrating sample magnetometer (VSM), and field-emission scanning and transmission electron microscopies (FE-SEM and TEM). Structural XRD and IR analyses revealed both samples to be composed of pure crystalline magnetite (Fe3O4). Morphological observations through FE-SEM and TEM proved the product to be spherical nanoparticles in the range of 10–15 nm. The presence of two coating polymers (i.e. PVP and PEI) on the surface of the electro-synthesized MNPs was proved by FTIR and DLS results. The percentage of the polymer coating (31.8%) on the MNPs surface was also determined based on DSC-TGA data. The high magnetization value, coercivity and remanence values measured by VSM indicated the superparamagnetic nature of both prepared MNPs. The obtained results confirmed that the prepared Fe3O4 nanoparticles had suitable physico-chemical and magnetic properties for biomedical applications. © 2017 Elsevier B.V.