Co-firing of coal with inexpensive secondary fuels such as petroleum coke is expected to increase in the near future in the EU given that it may provide certain economic and environmental benefits with respect to coal combustion. However, changes in the feed fuel composition of power plants may modify the bulk content and the speciation of a number of elements in fly ash and slag. Consequently, leachability of these byproducts also can be modified. This study is focused on identifying the changes in the environmental quality of co-fired fly ash and slag induced by a modification of the petcoke/coal ratio. Petcoke was found to increase the leachable content of V and Mo and to enhance the mobility of S and As. However, with the exception of these elements, the addition of this secondary fuel did not drastically modify the bulk composition or the overall leachability of the resulting fly ash and slag.