Titanium oxide (TiO2) has been widely investigated as a photocatalytic material for degradation of organic pollutant in waste water. However, nanosized granular TiO2 nanoparticles are hard to be recycled and re-utilized in water and many cause secondary pollution of water. Hence, we constructed a foam-like photocatalyst, which was composed of carbonaceous support: activated carbon nanotube foams and Ag-doped TiO2 nanoparticles through a method of a template synthesis and carbonization strategy. The as-prepared photocatalyst evidenced to be hierarchical macroporous and mesoporous and exhibited remarkable photocatalytic performance toward the degradation of unsymmetrical dimethylhydrazine under UV and visible light. The structure characterization and photocatalytic performance investigation confirmed that the enhanced photoresponse was attributed to the high efficiency of charge separation and the surface plasmon resonance effect of metallic Ag. The adsorption synergetic effect of the hierarchical porous structure also played an important role in photodegradation. The as-prepared photocatalyst showed great potential in the treatment of waste water containing organic pollutant.