This paper presents CO2 mitigation potential in the power sector of Thailand regarding to the Power Development Plan (PDP 2015) and Alternative Energy Development Plan (AEDP 2015). Renewable energy and advanced technology have the potential to play an important role in providing clean energy. The Long-range Energy Alternative Planning (LEAP) model is used to analyze future electricity demand, fuel consumption and CO2 emissions reduction in the long term planning during 2010-2050. Regarding to those plans, implementations of renewable energy and advanced technology are proposed for mitigation options. The mitigation scenarios offer sustainable potential of renewable technologies and advanced technologies such as solar, wind, biomass, nuclear, hydropower, hydrogen fuel cell, tidal, geothermal and fossil-fuel power plants with carbon capture storage (CCS). Four mitigation scenarios are modeled along with the BAU scenario. The Mitigation 1 (MIT01) scenario is the base-case mitigation scenario based on the target of PDP2015, which target of renewable energy is 19,634 MW in 2036. In the Mitigation 2 (MIT02) scenario, the technologies in the MIT01 plus new technologies such as hydrogen fuel cell, tidal and geothermal are implemented. Clean fossil fuel technologies with CCS, for example natural gas and coal technologies, are applied in the Mitigation 3 (MIT03) scenario. In the Mitigation 4 (MIT04) scenario as the peak CO2 scenario. Results show that, in the BAU scenario, electricity demand and CO2 emissions from the power sector will increase to 52,770 ktoe and 345,959 kt-CO2eq, respectively in 2050. By adopting mitigation options, total CO2 emissions in 2050 can be mitigated by 69.66% in MIT04, following by 50.83% in MIT02, 47.22% in MIT03, and 41.71% in MIT01 when compared to the BAU scenario. Moreover, regarding to the MIT04, Thailand can meet its peak CO2 emission by 2036.