The Czech Republic is gradually shifting toward a low-carbon economy. The transition process requires measures that will help to contain energy production and help to reduce emissions from the coal industry. Viable measures are seen in carbon capture technologies (CCTs). The main focus is on the environmental and economic comparison of two innovative CCTs that are integrated in the operational Czech energy units. The assessed scenarios are (1) the scenario of pre-combustion CO2 capture integrated into the gasification combined cycle (IGCC-CaL) and (2) the scenario of post-combustion capture by adsorption of CO2 by activated carbon (PCC-A). An environmental assessment is performed through a life-cycle assessment method and compares the systems in the phase of characterization, normalization, and relative contribution of the processes to the environmental categories. Economic assessment compares CCT via capture and avoided costs of CO2 and their correlation with CO2 allowance market trend. The paper concludes with the selection of the most suitable CCT in the conditions of the Czech Republic by combining the scores of environmental and economic parameters. While the specific case of IGCC-CaL shows improvement in the environmental assessment, the economic analysis resulted in favor of PCC-A. The lower environmental−economic combination score results in the selection of IGCC-CaL as the more viable option in comparison with PCC-A in the current Czech energy and economic conditions.