At present, milling of titanium based alloys for aerospace applications is mainly carried out with un-coated WC-Co carbide tools. The present work evaluates the chemical interaction of the Ti-6%Al-4%V alloy with these WC-Co commercial hardmetals. Strong decarburation induced by carbon diffusion to the Ti based alloy is observed at temperatures ranging from 750-1000°C. This reaction is responsible for the high adhesion found at the alloy-carbide interface. Different cathodic arc coatings have proved efficient in inhibiting such reaction and the associated adhesion to the Ti-6%Al-4%V alloy. Delamination induced by reaction between the Ti6Al4V alloy and AlTiN and TiAlCN coatings increases with the hot pressing temperature, being more severe for the AlTiN material. A lower bound of 44 J/m2 has been obtained for the interfacial fracture energy of cathodic arc PVD TiAlCN coatings on hardmetal substrates, this value being significantly higher than those previously reported for TiAlN materials.