Carbon Capture Utilization and Storage (CCUS) is a set of technologies aimed at capturing carbon dioxide (CO2) emissions from point-source emitters to either store permanently or use as a feedstock to produce chemicals and fuels. In this paper, the potential benefits of CCUS integration into the energy supply sector are evaluated from a Life Cycle Assessment (LCA) perspective by comparing two different routes for the CO2 captured from a natural gas combined cycle (NGCC). Both the complete storage of the captured CO2 and its partial utilization to produce dimethyl ether are investigated. Moreover, the assessment is performed considering the region-specific features of two of the largest CO2 emitters in Europe, namely Italy and Poland. Results shows that the complete storage of the captured CO2 reduces Global Warming Potential (GWP) by ~89% in Italy and ~97%, in Poland. On the other hand, the partial utilization of CO2 to produce dimethyl ether leads to a decrease of ~58% in Italy and ~68% in Poland with respect to a comparable reference entailing conventional dimethyl ether production. A series of environmental trade-offs was determined, with all the investigated categories apart from GWP showing an increase, mainly connected with the higher energy requirements of CCUS processes. These outcomes highlight the need for a holistic-oriented approach in the design of novel implemented configurations to avoid burden shifts throughout the value chain.