Abstract: An extended overview of the chemical composition of biomass was conducted. The general considerations and some problems related to biomass and particularly the composition of this fuel are discussed. Reference peer-reviewed data for chemical composition of 86 varieties of biomass, including traditional and complete proximate, ultimate and ash analyses (21 characteristics), were used to describe the biomass system. It was shown that the chemical composition of biomass and especially ash components are highly variable due to the extremely high variations of moisture, ash yield, and different genetic types of inorganic matter in biomass. However, when the proximate and ultimate data are recalculated respectively on dry and dry ash-free basis, the characteristics show quite narrow ranges. In decreasing order of abundance, the elements in biomass are commonly C, O, H, N, Ca, K, Si, Mg, Al, S, Fe, P, Cl, Na, Mn, and Ti. It was identified that the chemical distinctions among the specified natural and anthropogenic biomass groups and sub-groups are significant and they are related to different biomass sources and origin, namely from plant and animal products or from mixtures of plant, animal, and manufacture materials. Respective chemical data for 38 solid fossil fuels were also applied as subsidiary information for clarifying the biomass composition and for comparisons. It was found that the chemical composition of natural biomass system is simpler than that of solid fossil fuels. However, the semi-biomass system is quite complicated as a result of incorporation of various non-biomass materials during biomass processing. It was identified that the biomass composition is significantly different from that of coal and the variations among biomass composition were also found to be greater than for coal. Natural biomass is: (1) highly enriched in Mn > K > P > Cl > Ca > (Mg, Na) > O > moisture > volatile matter; (2) slightly enriched in H; and (3) depleted in ash, Al, C, Fe, N, S, Si, and Ti in comparison with coal. The correlations and associations among 20 chemical characteristics are also studied to find some basic trends and important relationships occurring in the natural biomass system. As a result of that five strong and important associations, namely: (1) C–H; (2) N–S–Cl; (3) Si–Al–Fe–Na–Ti; (4) Ca–Mg–Mn; and (5) K–P–S–Cl; were identified and discussed. The potential applications of these associations for initial and preliminary classification, prediction and indicator purposes related to biomass were also introduced or suggested. However, future detailed data on the phase–mineral composition of biomass are required to explain actually such chemical trends and associations.