We investigated in detail the structural, chemical, and magnetic properties of Fe at the interface with MgO. The samples were grown by molecular-beam epitaxy and analyzed by using reflection high-energy electron diffraction, scanning tunneling microscopy, Auger electron spectroscopy, x-ray photoemission spectroscopy (XPS), x-ray-absorption spectroscopy (XAS), and x-ray magnetic circular dichroism (XMCD) measurements. We discuss the presence or absence of C and O contaminants at the surface of the metallic film. We actually show that when growing the first Fe layer on the initial MgO substrate, a carbon contamination at the surface of the annealed Fe layer is observed leading to a C(2×2) surface structure. We propose a method to eliminate this carbon contamination and to get interfaces free of carbon. On the other hand, we observed that the reactivity of the Fe surface to oxygen contamination is greatly influenced by the presence of carbon or absence on the surface. The influence of oxygen adsorption at the Fe surface on the MgO growth will also be discussed. Concerning the hybridization between Fe or Co with MgO, XPS, and XAS-XMCD analyses clearly demonstrate that the charge transfer is weak, and that the magnetization at the interface is larger than in bulk (3μB/at for Fe). With such clean interfaces, reproducible magnetoresistance equal to 160% are obtained on Fe∕MgO(3nm)∕Fe(001) 100×100μm2 tunnel junctions at room temperature in our laboratory. Finally, we show that pollution at the bottom Fe∕MgO interface modify drastically spin-dependent tunneling properties.