This study evaluates the occurrence of decoupling of CO2 emissions from Gross Domestic Product (GDP) in South Africa (SA) for the period of 1990 to 2012 by using the Organization for Economic Cooperation and Development (OECD) and Tapio methods, and identifies the primary CO2 emissions driving forces by the Kaya identity. The results showed a strong decoupling during the period of 2010–2012, which is considered as the best development situation. In 1994–2010 SA had a weak decoupling; while during the period 1990–1994, the development in SA presented an expansive negative decoupling state. The comparison of the OECD and Tapio’s methods showed well-correlated results but differed in their applications; however, the OECD method appeared as the simpler one. The results of Kaya identity demonstrated that the increase in population, GDP per capita and deteriorating energy efficiency were the main primary driving forces for the increase of CO2 emissions. It is suggested that SA can expand the share of renewable energy and promote green energy technology in addition to better strategies of the demand side management (DSM) to raise the efficiency of energy consumption as well as CO2 emission reductions. The methods used in this research can be applied to other countries with similar situations to evaluate the trends of energy consumption and CO2 emissions and an aid to decision-making tool for better sustainable development.