Highly corrosion and wear resistant thermally sprayed chromium carbide (Cr3C2) based cermets coatings are nowadays a potential highly durable solution to allow traditional fluidised bed combustors (FBC) to be operated with ecological waste and biomass fuels. However, the heat input of thermal spraying processes causes carbide dissolution in the metal binder. This alters the coating structure and forms carbon saturated amorphous and nanocrystalline metastable areas, which can affect the behaviour of the materials under the corrosive chlorides containing environment of the flue gases. This study analyses the effect of carbide dissolution in the metal matrix of MMC coatings and its effect on the onset of chlorine induced high temperature corrosion. Four Cr3C2-NiCrMoNb coatings were thermally sprayed with high-velocity air-fuel (HVAF) and high-velocity oxygen-fuel (HVOF) spray processes in order to obtain microstructures with increasing amount of carbide dissolution in the metal matrix. The specimens were heat treated in an inert argon atmosphere at 700°C for 5 hours to induce secondary carbide precipitation. As-sprayed and heat-treated self-standing coatings were covered with KCl and their corrosion resistance was investigated with thermogravimetric analysis (TGA) at 550°C for 4 hours. High carbon dissolution in the metal matrix appeared to be a detrimental factor in the initial stage of corrosion. The microstructural changes induced by the heat treatment hindered the corrosion onset in the coatings. Moreover, an optimal amount of oxides and melting degree seemed beneficial.