Vanadium-containing mesoporous silica molecular sieve (V proportional to HMS) with tetrahedrally coordinated V-oxide species (V(V)O4) has been prepared by a modified surfactant-templating method, consisting of an addition of surfactant to a mixture of water, alcohol, and Si and V precursors followed by calcination. The V-HMS demonstrates high photocatalytic activity even in the presence of water, while other V proportional to HMS's prepared by conventional templating methods and V/HMS prepared by an impregnation method show almost no activity owing to hydrolysis of the (VO4)-O-V species. ESR and photoluminescence measurements reveal that the modified templating method creates (VO4)-O-V species confined within a silica layer, while other methods create (VO4)-O-V species exposed on silica surface. The former (VO4)-O-V species are highly stabilized by the confinement within the silica, thus suppressing the hydrolysis. Another notable property of the confined (VO4)-O-V species is the higher photocatalytic activity even without water, despite their confined structure. This is explained by higher electrophilicity and longer lifetime of the excited-state (VO4)-O-V species ((VO4)-O-IV*) derived from their distorted structure. The obtained findings suggest potential use of the modified surfactant-templating method for synthesis of stable and recyclable V-containing mesoporous silica with high photocatalytic activity.