A hierarchical meso-/macroporous titanium phosphonate (TPPH) hybrid material was prepared via a simple surfactant-assisted process with the use of the precursor tetrabutyl titanate and 1-hydroxy ethylidene-1,1-diphosphonic acid. The prepared hybrid TPPH presented amorphous phase, exhibiting a hierarchical macroporous structure composed of mesopores with a pore size of 2.0 nm. The BET surface area is 256 m2/g. The hydroxyethylidene-bridged organophosphonate groups were homogeneously incorporated in the network of the hierarchical porous solid, as revealed by FT-IR, MAS NMR, XPS, and TGA measurements. The optical properties and photocatalytic activity of the hierarchical TPPH material were investigated in comparison with those of hierarchical porous titanium phosphate and pure mesoporous titania materials, showing superiority of the inorganic-organic hybrid framework, suggesting promising photocatalysts for wastewater cleanup.