By modification of parameters in plasma spraying it is possible to alter porosity of the deposits only in a relatively small range. Industrial applications may require to adjust the porosity in wider range, to double or triple the original value in some cases. Such changes can be achieved only by special procedures. One of them is plasma spraying of ceramic/metal deposit followed by removal of the metal within the coating. The material removal is performed by dissolving, by leaching or by its extraction with an appropriate process. The paper describes preparation of very porous Cr2O3 coatings by this method from a composite Cr2O3/Al deposit. The initial porosity of approximately 13% (total porosity) was increased to 37% or 51% respectively by changing the initial volume of aluminum in the ceramic/metal plasma-sprayed composite. The discussion is complemented by observation of the resulting coating structure and detailed characterizations of the pore structure and porosity.