We report on the preparation, by means of pulsed laser ablation deposition, of trilayers of nominal composition Cr/SmCo5/Cr//Si with thicknesses in the order of 250/240/125nm, respectively. According to the results of the structural, chemical and magnetic characterizations performed in our as-deposited samples, the Sm–Co layer was structurally amorphous, exhibited abrupt compositional interfaces with the capping and buffering layers, and coercivities of a few hundreds of Oe. Magnetic hardness was developed upon submitting the samples to current anneals under vacuum at temperatures in the range of 540–670°C. The hardening process was followed in detail by correlating the phase distribution, the nature of the interlayer atomic diffusion processes, the occurrence of textures and the temperature dependence of the coercive force. From our results we conclude about (i) the occurrence of a large degree of Co diffusion/segregation, which results in the detection, from the diffraction and magnetometric results, of the presence of CoCr alloys in the treated samples, and (ii) the close correlation, evidenced from the fits of the temperature dependence of the coercive force to the micromagnetic model, between the coercivity optimization and the crystallinity enhancement of the SmCo5 grains.