The present study characterizes the surface of AISI 4140 steels exposed to the paste-boriding process. The formation of Fe2B hard coatings was obtained in the temperature range 1123–1273 K with different exposure times, using a 4 mm thick layer of boron carbide paste over the material surface. First, the growth kinetics of boride layers at the surface of AISI 4140 steels was evaluated. Second, the presence and distribution of alloying elements on the Fe2B phase was measured using the Glow Discharge Optical Emission Spectrometry (GDOES) technique. Further, thermal residual stresses produced on the borided phase were evaluated by X-ray diffraction (XRD) analysis. The fracture toughness of the iron boride layer of the AISI 4140 borided steels was estimated using a Vickers microindentation induced-fracture testing at a constant distance of 25 μm from the surface. The force criterion of fracture toughness was determined from the extent of brittle cracks, both parallel and perpendicular to the surface, originating at the tips of an indenter impression. The fracture toughness values obtained by the Palmqvist crack model are expressed in the form KC(π/2) > KC > KC(0) for the different applied loads and experimental parameters of the boriding process.