A new strategy to synthesize a highly efficient CO2 capturer by incorporating tetraethylenepentamine (TEPA) into as-synthesized MCM-41 (AM) is reported. The amine guest can be distributed in the micelle of the support, forming a web within the mesopore to trap CO2 molecules and resulting in a high adsorption capacity for CO2 up to 237 mg g−1. Four samples of the as-synthesized MCM-41 with a different amount or type of surfactant are employed as supports to investigate the influence of micelles on the CO2 adsorption, and the spokelike structure of the micelle in the channel of the support is proven to be essential to the distribution of guest amine. Among these supports, the AM sample is the most competitive due to the advantages of energy and time saving in preparation of the support along with the resulting higher CO2 adsorption capacity. At the optimal loading of 50 wt % TEPA, the AM-50 sample exhibits a high adsorption capacity of 183 mg g−1 in the sixth adsorption cycle at 5 % CO2 concentration.