Biomass has become an increasingly important resource for energy generation. The influence of the chemical composition on the heating value of biomass has not been a thoroughly studied subject, as shown by a bibliometric analysis. It is well known that the heating value of lignin is significantly higher (23.26–25.58 MJ/kg) than that of polysaccharides (18.6 MJ/kg), while extractives often have HHVs over 30 MJ/kg, depending on their oxidation levels. Therefore, the proportions of the chemical components in biomass determine its HHV. Softwoods generally have higher HHVs than hardwoods due to their higher contents of lignin and lipophilic resin. Ashes are incombustible, and a high ash content leads to a lower HHV in biomass. Several models have been proposed to correlate the heating values and chemical compounds of biomass, but the most accurate models are based on the lignin from extracted samples, while good correlations between lignin and extractives have also been reported. No good correlations have been obtained with polysaccharide compounds.