Homogeneous hybrids in which iron oxide nanoparticles are entrapped within polymer structure are of interest for their potential applications in biomedical field, such as diagnostic, therapeutic and theranostic purposes. For this reason, hybrid nanomaterials based on branched polyethyleneimine (PEI) and iron oxide with different ratios were synthesized in a single step by hydrothermal procedure at high pressure and low temperature. Iron oxide is formed in the presence of branched PEI and the interaction between them takes place in the reaction medium. The influence of synthesis parameters on the hybrid formation, as well as chemical and structural properties was studied by means of FTIR, DSC-TG, HRTEM, electron paramagnetic resonance (EPR), magnetic measurements (SQUID) and Fe-57 Mossbauer analyses. It has been shown that synthesis parameters influence thermal stability and morphology of the hybrids. FeO(OH) crystallites of 2-5 nm are formed. Iron oxyhydroxide nanoparticles strongly entrapped in PEI structure are obtained. The low and distributed values of the specific spontaneous magnetisation in samples prepared under the same pressure conditions support the presence of very fine FeO(OH) nanoparticles, which formation and magnetic properties are depending on the mass ratio between iron oxide and PEI. (C) 2015 Elsevier B.V. All rights reserved.