Climate change and CO2 mitigation have become increasingly important environmental issues. Recently Thailand has proposed policies on GHG mitigation such as Thailand’s Nationally Appropriate Mitigation Action (NAMA), which aims at GHG mitigation in the energy sector. This study used the computable general equilibrium (CGE) model, called “AIM/CGE” model, to analyse GHG mitigation measures under emission trading and carbon capture and storage (CCS) technology in Thailand. Results show that the international free emission trading policy can drive more GHG reduction by decreasing energy supply and demand, and increasing prices of emissions. The CCS technologies would balance emission reduction but they would reduce energy efficiency improvement and renewable energy utilization. In the energy security aspect, the policy options in this study would improve energy security, energy import dependency, and co-benefits of GHG mitigation in forms of improving local air quality. Results are also helpful to GHG mitigation policy in developing countries.