This work presents a novel approach to enhance the gasification reactivity of highly unreactive petroleum coke by purposely promoting its synergistic interactions with selected carbonaceous materials. To achieve this, an Australian coal and gum wood were chosen for co-processing with petroleum coke. It was found that the addition of gum wood resulted in more significant enhancement in the gasification reactivity of petroleum coke, which was attributed to the combined influence of the catalytic effect of alkali and alkaline earth metals (AAEM) in gum wood and the unique features of biochar, such as high surface area, more active sites, low crystalline index, etc. It confirmed that interactions between an unreactive fuel, such as petroleum coke, and selected carbonaceous materials could be capitalized on to enhance overall reactivity of the blends. This approach helps improve the conversion efficiency of unreactive fuels such as petroleum coke and therefore promotes their large-scale utilization.