Silver/titania composite hollow spheres were first synthesized through an in-situ chemical reaction using functional-grouped carbon spheres as the template in this study. The prepared samples were characterized through an X-ray diffraction, N2 adsorption–desorption, scanning electron microscopy, transmission electron microscopy and UV–Vis spectrophotometer. The photocatalytic activity of as-prepared samples was evaluated by photocatalytic decolorization of Methyl orange (MO) aqueous solution at ambient temperature under UV light. We found a structure with an optimal Ag:TiO2 composition that exhibited a photodecomposition rate constant more than twice as high as titania hollow spheres lacking silver, and over three times higher than a commercial photocatalyst.