Coal-fired thermal power plants are the major source of CO2 emission among fossil fuel power plants. In thermal power plants, coal combustion produces flue gas containing a number of gases including hazardous pollutants, such as CO2, mercury (Hg), sulfur dioxide (SO2), and oxides of nitrogen (NOx). Among all, CO2 is the largest contributor to global warming. CO2 capture and separation are therefore essential to keep the environment safe and secure. The present paper delineates the existing literature to examine the current status of various methods and technologies used for CO2 capture and separation from thermal power plant flue gas. Various emerging technologies like, chemical-looping combustion, integrated gasification combined cycle, enzyme based separation, dual-alkali absorption approach, facilitated transport membrane, hydrate based separations, mixed matrix membrane and, calcium looping are also thoroughly discussed. ► We critically examined existing literature on current status of various technologies of CO2 capture and separation. ► New emerging technologies were discussed in the paper. ► The major improvements to existing processes was needed for better overall removal efficiency of CO2.