Integral to the performance of high-velocity oxygen-fuel (HVOF) coatings is the thermo-mechanical interaction associated with the thermal misfit, or differences in thermal expansion coefficients (CTEs), between coating and substrate. This investigation reports results on the microstructures, chemical phase content, coating-substrate misfit residual stress, and wear resistance. For this purpose a systematic characterization of WC-Co sprayed coatings on a number of substrates covering a range of CTE values were pursued for both the as-coated and heat-treated conditions. The neutron diffraction technique in conjunction with sub-millimeter sized gauge volumes enabled depth-resolved studies of the stress in the coatings and substrates by paying special attention to the determination of the stress contribution attributed by the final spray process. In the as-coated condition the stress values in the coatings were compressive for CTEs larger than that of WC-Co and tensile for CTE lower than WC-Co. Wear resistance increased for increased compressive stress and macrohardness. In the heat-treated condition, this trend became enhanced due to increased compressive stress in the coatings. (C) 2013 Elsevier B. V. All rights reserved.