This article describes the effects of surface controlled decarburization on the structure of a nitrided steel. Samples of quenched and tempered 40CrMo4 steel were decarburized by air heat treatment (800–900°C) at different depths and submitted to gaseous nitriding. The microstructure of surface layers after decarburization and nitriding were investigated by optical (OM) and scanning electron microscopy (SEM). The nitrogen and carbon profiles in the diffusion layers were determined by a scanning electron microscope equipped with a wavelength dispersive spectrometer (EPMA-WDS). The effect of nitriding was determined by microhardness measurements. The increasing of time and temperature of decarburization slightly affect the surface hardness values, while case hardness depths decrease. In all the specimens, the nitriding depth, as determined by the WDS nitrogen profile, is larger than the one determined by the hardness profile.