The energy balance of Greece is strongly dependent on imported oil. The rather late introduction of natural gas has increased the diversity of the energy mix while the share of renewable sources in primary energy supply still needs to increase according to the existing potential. Yet, Greece as one of the most of the EU developed countries encounters a serious task: the need to increase its electricity production of almost 5% per year but at the same time to reduce the CO2 emissions according with the National and International (20-20-20) regulations and allocation plans. Therefore reducing CO2 emissions has become a major priority for national government. In addition, from 2013, there will be the full implementation of the wholesale market in the European Trading Scheme (ETS) which is currently in the last stages of a transition phase.In Greece electricity is mainly generated from lignite, thus making the electricity sector one of the main contributors to GHG emissions with a level above 40% of the total country and higher than the corresponding average of the rest of the EU countries. The possible implementation of Carbon Capture and Storage (CCS) technologies would then become very decisive due to the large use of the lignite as fuel in the country electricity mix. CCS technology has the potential of increasing the flexibility on the achievement greenhouse gas emissions reduction by allowing to continue to use fossil fuels, which still guarantees feasibility in the energy sector. This work presents a roadmap with the modeling of the main technologies associated to the CCS and its implementation into the Greek energy system considering existing National and International Strategic energy plans under different scenarios. The implementation of CCS technologies would have a large influence on the national electrical power production, having the responsibility for large shares of the emissions reduction that can potentially achieved in this sector. For this purpose, TIMES (The Integrated MARKAL/EFOM System) has been chosen as the principal tool for building a techno-economic model of the Greek energy system and its possible evaluation over time (2040).