We report the synthesis of Fe nanocrystals (similar to 9 nm) in an anhydrous media, formamide, using poly(N-vinyl-2pyrrolidone) (PVP) as a protecting agent. The morphology, structure, and composition of the PVP-coated Fe nanocrystals are studied by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and FT-Raman spectroscopy. The surface properties of the PVP-coated Fe nanocrystals are studied by electrochemistry and micro-surface- enhanced Raman scattering (mSERS) using pyridine as a probing molecule. The PVP-coated Fe nanocrystals, when immobilized on an electrode substrate, display very good electrocatalytic activities in the selective reduction of H2O2 in the presence of oxygen and in the oxidation of NO.