Mitigation of CO2 emissions has become a top-question in international and national arenas, likewise on the city level. Existing CO2 mitigation measures are primarily oriented towards wider deployment of low-carbon technologies of renewable energy sources and energy efficiency measures, focusing on energy production, distribution and energy use sectors, as well as the transport sector. Due to higher CO2 reduction efficiency and the cost aspect, the direct CO2 mitigation options currently applied are mostly oriented on large scale CO2 generators. Meanwhile the rural, sparsely populated regions already suffer from a lack of innovative industrial economic activities, inhabitant’s migration to urban areas and mostly involved in agriculture, land use and forestry activities. They are also “saved” by the public authorities from targeted CO2 emissions mitigation actions, therefore, the understanding of processes within rural CO2 economy sectors, factors, interconnections and effects to the environment and nature quality and finally guidelines to future actions are crucial. To analyse CO2 valorisation options for regional development, a multi-modelling approach combining literature review, an indicator analysis method and a multi-criteria decision-making analysis were used. As a result, CO2 valorisation options and key performance indicators were defined and multi-criteria analysis for regional decarbonization scenarios were performed.