HVOF-sprayed WC–10wt%Co–4wt.%Cr coatings were obtained using experimental feedstock powders (manufactured by spray-drying + sintering), containing nanometric carbide particles. Three reference coatings were also deposited using commercially-available powders containing sub-micrometric carbide particles. The coatings obtained from nanostructured powders, although affected by decarburisation phenomena, contained very fine carbide particles (~200 nm size). Those obtained from commercially-available powders simultaneously exhibited sub-micrometric (~400 nm size) and micrometric carbide particles, and were much less decarburised. Sliding wear tests performed at room temperature against sintered Al2O3 balls showed the occurrence of brittle fracture wear (detachment of near-surface material by local brittle cracking) on the nanostructured coatings, which were embrittled by decarburisation. The reference coatings, by contrast, exhibited either ductile wear behaviour (plastic deformation, pull-out of single carbide particles) or a mix of both ductile and brittle wear mechanisms. When the decarburisation of the nanostructured coatings was not too extensive, their wear loss was comparable to that of the reference ones. At 500 °C, the wear behaviour of all coatings was dominated by abrasive grooving, on account of thermal softening. The most decarburised nanostructured coatings, however, still experienced brittle cracking as well.