The present investigation deals with the definition of a new eco-friendly alternative to pretreat Co-cemented tungsten carbide (WC-Co) substrates before diamond deposition by hot filament chemical vapor deposition (HFCVD). In particular, WC-5.8 wt %Co substrates were submitted to a thermal treatment by a continuous wave-high power diode laser to reduce surface Co concentration and promote the reconstruction of the WC grains. Laser pretreatments were performed both in N(2) and Ar atmosphere to prevent substrate oxidation. Diamond coatings were deposited onto the laser pretreated substrates by HFCVD. For comparative purpose, diamond coatings were also deposited on WC-5.8 wt %Co substrates chemically etched by the well-known two-step pretreatment employing Murakami's reagent and Caro's acid. Surface morphology, microstructure, and chemical composition of the WC-5.8 wt %Co substrates after the different pretreatments and the deposition of diamond coatings were assessed by surface profiler, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction analyses. Wear performance of the diamond coatings was checked by dry sliding linear reciprocating tribological tests. The worn volume of the diamond coatings deposited on the laser pretreated substrates was always found lower than the one measured on the chemically etched substrates, with the N(2) atmosphere being particularly promising.