Abstract Anthropogenic material and energy flows are considered to be the major cause of many environmental problems humans face today. In order to measure material and energy flows, and to mitigate related problems, the technique of material flow and energy flow analysis has been conceived. The aim of this article is to use material and energy flow accounting approaches to quantify the amount of biomass that is available, but that so far has not been used for energy purposes in Slovakia and the Czech Republic and to calculate how much consumed fossil fuels and corresponding CO2 emissions can be saved by utilising this biomass. Based on the findings presented, 3544 kt/yr of the total unused biomass in Slovakia could replace 53 PJ/yr of energy from fossil fuels and 6294 kt/yr of the total unused biomass in the Czech Republic could replace 91 PJ/yr of energy. Such replacement could contribute to a decrease in total CO2 emissions by 9.2% in Slovakia and by 5.4% in the Czech Republic and thus contribute to an environmental improvement with respect to climate change.