The energy potential of wood biomass is significantly shaped by its chemical composition. Analyzing the chemical composition of wood biomass and understanding the correlations between these parameters and wood combustibility are essential stages in the selection process of Eucalyptus clones tailored for firewood production and energy generation. In this study, we aimed to evaluate the impact of chemical composition on the direct combustibility of Eucalyptus clones. We examined the structural chemical composition and conducted proximate analysis, including fixed carbon, volatile material, and ash, to investigate the relationship between proximate composition and wood combustibility parameters. Our findings revealed significant correlations between wood chemical composition and combustibility parameters. In particular, lignin content, ethanol-soluble extractives, and xylose demonstrated inverse relationships with the parameters of maximum combustion rate, combustion characteristic index, and ignition index. Conversely, holocellulose content, cold-water-soluble extractives, and glucose exhibited direct correlations with the same combustibility parameters. Furthermore, fixed carbon and volatile matter contents demonstrated direct and inverse correlations, respectively, with ignition temperature. These findings have significant implications for enhancing the efficiency and sustainability of biomass energy production.