In this study, a novel Mo-containing hierarchical ordered macro-mesoporous material, Mo-MM-SBA-15-4-30, was synthesized via a facile dual-templating technique. The formation of a well-defined macro-mesoporous structure was verified by N2 adsorption–desorption curves, SEM and TEM observations. Moreover, the characterization results of XPS, ICP-AES, EDX demonstrated the successful incorporation of molybdenum species into the bulk hierarchical macro-mesoporous material Mo-MM-SBA-15-4-30. A series of comparative studies revealed that this hierarchical macro-mesoporous material Mo-MM-SBA-15-4-30 exhibited higher catalytic activities for the epoxidation of linear α-olefin than Mo-containing mesoporous silica. Turnover number of linear α-olefins was also significantly enhanced due to the hierarchical macro-mesoporous structure of Mo-MM-SBA-15-4-30 in which the presence of mesoporous channels shortened diffusion limitation. Additionally, the catalyst Mo-MM-SBA-15-4-30 exhibits the excellent catalytic stability.