This study focuses on the effects of a surface mechanical attrition treatment on the structural and mechanical behavior of arc-sprayed Ni–Cr coatings deposited on steel substrates. The surface of the as-sprayed and SMATed coatings was characterized by X-ray diffraction, Scanning Electron Microscopy, and non-contact profilometry. The coating porosity was evaluated by using image analysis software. The residual stresses were determined using X-ray diffraction with the sin²ψ. Indentation tests were carried out on the cross sections of the different coatings to evaluate their hardness. The wear properties of the coatings were assessed using a pin-on-disk tester at ambient temperature without lubrication. The results showed that surface mechanical attrition treatment (SMAT) induced a grain refinement on the coating surface due to severe plastic deformation, which was associated with a significant improvement of the mechanical properties.