In 2013, the electricity sector was the largest source of South Africa’s CO2 emissions, accounting for about 60% of its total. South Africa (SA) is one of the highest CO2 emitters on a per capita basis when compared to many developed and developing countries. For a better understanding of the driving forces leading the electricity-related CO2 emission per person, this paper applies the Log Mean Divisia Index (LMDI) to analyze the influence of the factors which ruled electricity generation-related CO2 emission in SA over the period 1990–2013. We focused on coal which is the dominant fuel used in SA for electricity generation. The results show that the electricity generation intensity effect plays the dominant role in decreasing CO2 emissions. However, the effect of economic activity is the major determinant that contributes to increasing CO2 emissions. In order to reduce its greenhouse gas emissions levels, meet the agreement of the COP21 agreement, and fight against CO2 emissions per-capita associated with electricity generation, it is recommended that SA’s government should improve the efficiency of its existing electricity power generation plants and expand more of its renewable energy sources (nuclear included).