This study uses hierarchical structure methods (minimal spanning tree, (MST) and hierarchical tree, (HT)) to examine the hierarchical structures of the carbon dioxide emission from the 84 countries by three main sectors, namely electricity/heat, manufacturing/construction and transportation sectors. We obtain the topological properties among the countries based on carbon dioxide emission over the periods of 1971-2012. We also perform the bootstrap techniques to investigate a value of the statistical reliability to the links of the MSTs. The results of the topologies structural of these trees are as follows: (i) We identified different groups of countries according to their economic growth and geographical location. (ii) Our results show that the high income and low energy consuming country groups are more important within the network.