In this work, mesoporous silica (MCM-41) and a cobalt-incorporated catalyst (Co-MCM-41) were prepared using colloidal silica Cab-O-Sil, sodium silicate and tetraethylorthosilicate (TEOS) as the silica sources and cobalt nitrate as the cobalt source. Their physicochemical properties were analyzed, and their catalytic performance for the synthesis of single-wall carbon nanotubes (SWCNT) during chemical vapor deposition (CCVD) of methane was evaluated. When Cab-O-Sil was used, it was possible to incorporate 3% (nominal) cobalt with a good dispersion and without losing mesoporosity, resulting in minimal formation of superficial cobalt oxide. In contrast, the other catalysts product superficial cobalt oxide, according to the temperature programmed reduction (TPR) analysis. Co-MCM-41 prepared using Cab-O-Sil showed the best performance during the formation of SWCNT with a good regularity and selectivity without forming multi-wall carbon nanotubes or amorphous carbon structures.