Well-ordered lamellar mesoporous molybdenum(V/VI) oxides were prepared using gemini surfactant [C 14 H 29 N + (CH 3 ) 2 -(CH 2 ) 2 -N + (CH 3 ) 2 -C 14 H 29 ]·2Br − (denoted C 14-2-14 ) as the structure-directing agent and ammonium heptamolybdate tetrahydrate (NH 4 ) 6 Mo 7 O 24 ·4H 2 O as the precursor. The samples were characterized by X-ray powder diffraction, high-resolution transmission electron microscopy and N 2 adsorption–desorption. A possible arrangement of gemini surfactant in the interlayer space of molybdenum oxide was proposed. Gemini surfactant possessed better self-assembly ability than monovalent surfactant to form well-ordered mesostructures in mild conditions. The lamellar mesopore structure is retained after removal of the gemini surfactant by soxhlet extraction. The cheap and air-stable precursor provided an advantageous access to synthesize mesoporous transition metal oxides.