Thailand’s commitment to achieving its CO2 emissions reduction policy by 2027 and attaining carbon neutrality by 2070 is a critical component of international strategic efforts to mitigate climate change. One proposed method of implementing these plans involves capturing CO2 emissions and storing them permanently underground. As an initial step, this study proposes using flue gas emissions from the post-combustion process of a 9.9 MWe biomass-fired power plant (BFPP) as a case study, followed by an assessment of potential power plants to evaluate the feasibility of launching a new green campaign aligned with the Sustainable Development Goals (SDG) 13th. This paper presents a technical and economic assessment of integrating a BFPP facility in Thailand with CO2 capture and liquefaction technology. An equilibrium-based process model for CO2 capture, compression, and liquefaction was simulated using ASPEN Plus software, while both CAPEX and OPEX were evaluated using the Enhanced Detailed Factor (EDF) method. Results indicate that the levelized cost of CO2 capture (LCOC) ranges from US$103/tCO2 to US$125/tCO2. The energy demand for the CO2 capture, compression, and liquefaction system reduced the overall efficiency of the plant by 11% at a 97% capture rate. Installing both CO2 capture and liquefaction units at BFPP facilities could play a significant role in achieving Thailand’s emission reduction targets. However, the successful execution of these measures requires a well-structured and supportive policy framework. This paper offers valuable insights into the potential of CO2 capture technology in Thailand’s BFPP sector, contributing to its sustainability goals.