Recent studies demonstrated a relationship between mass burn rates of straight-grade cigarettes and heats of combustion of the tobacco materials. In the present work, relationships between measured heats of combustion and elemental composition of the tobacco materials were further analyzed. Heats of combustion measured in oxygen were directly correlated with the carbon and hydrogen content of the tobacco materials tested. Ash content of the materials was inversely related to the heats of combustion. The water insoluble residues from exhaustively extracted tobacco materials showed higher heats of combustion and higher carbon content than the non-extracted materials, confirming a direct relationship between carbon content and heat of combustion. A value for the heat of formation of tobacco was estimated (1175 cal/g) from the heat of combustion data and elemental analysis results. The estimated value for heat of formation of tobacco appears to be constant regardless of the material type. Heat values measured in air were uniformly lower than the combustion heats in oxygen, suggesting formation of CO and other reaction products. Gases produced during bomb calorimetry experiments with five tobacco materials were analyzed for CO and CO2 content. When the materials were burned in oxygen, no CO was found in the gases produced. Measured heats of combustion matched estimates based on CO2 found in the gas and conversion of the sample hydrogen content to water. Materials burned in air produced CO2 (56% to 77% of the sample carbon content) and appreciable amounts of CO (7% to 16% of the sample carbon content). Unburned residue containing carbon and hydrogen was found in the air combustion experiments. Estimated heat values based on amounts of CO and CO2 found in the gas and water formed from the hydrogen lost during combustion in air were higher than the measured values. These observations indicate formation of products containing hydrogen when the materials were burned in air. CO and CO2 formation during combustion in air were related to the composition of the tobacco materials. Materials with high carbon and low ash content showed evidence of higher CO2 formation. Amounts of unburned residue also varied with material composition. Thus, energy released during tobacco combustion in air is related to material-dependent formation of reaction products in addition to the carbon oxides and to the quantity of unburned material.