Polyol made from about 10 nm sized maghemite nanoparticles was functionalized by a hydrophilic catechol derivative, namely, dopamine. Infrared spectroscopy confirmed the grafting, whereas X-ray diffraction and transmission electron microscopy did not show either structural or microstructural change on the iron oxide particles. 57Fe Mössbauer spectrometry allowed, giving a quantitative assessment of the bonding preferences of dopamine on the iron oxide surfaces, the π-donor character of this ligand to be experimentally evidenced for the first time. These results are supplemented by ab initio modeling, expanding on previous work by considering various iron oxide surfaces and orientations. Perspectives of the work are discussed.