A transparent TiO2-C@TiO2-C free-standing film is synthesized. The film preserves 3D reticulate microstructure of cellulose paper. The flower-like TiO2-C particle layers are intimately inhered to TiO2-C fiber. Introduction of secondary carbon promotes the generation of Ti-O-C bonds. TiO2-C@TiO2-C film exhibits enhanced photocatalytic activity for MB degradation.