In Venezuela, the hydrocarbon refining industry produces approximately 400 TPD of flexicoke, a by-product of the FlexicokingTM process, a technology that thermally transforms heavy oils to lighter more valuable products. This solid material concentrates large amounts of vanadium and nickel, and it is usually traded for power generation or metal recovery. However, the indigenous metals in this carbonaceous solid present inherently an excellent dispersion and therefore some potential for complementary catalytic applications. For solid carbonaceous feedstocks, V has been reported to enhance combustion while Ni has shown a good activity to promote gasification with steam for the generation of valuable synthesis gas. However, most conclusions have been extracted from experiences at laboratory scale with synthetic samples, and not with real world ones collected from commercial plants. In this contribution, a real flexicoke sample obtained from a refinery is lixiviated with base and acid to allow the selective removal of each metal, and the assessment of the activity of the individual elements towards the promising gasification with steam is monitored in a thermogravimetric analyzer coupled to a quadrupole mass spectrometer for evolved gas analysis. Analysis by XPS permits the correlation of surface metal composition with catalytic activity monitored during the course of the test reaction. It is shown that Ni catalytically enhances the conversion of the flexicoke to CO and H2 at a temperature much lower than the one observed thermally both in the original sample and in the fully demetalized carbon matrix. In addition, Ni activity is inhibited in the presence of V, presumably due to the formation of a deactivating layer on top of the Ni surface and, therefore, V must be selectively removed from the original material for the catalysis to take place.