Porous TiO2 films decorated with Bi2O3 nanoparticles are fabricated via alkali-hydrothermal of titanium (Ti) plate by varying the reaction time. The amorphous TiO2 is transformed into anatase after annealing the films at 500 degrees C in air. The p-type Bi2O3 nanoparticles are successfully assembled on the surface of porous n-type TiO2 films through the ultrasonic-assisted successive ionic layer adsorption and reaction (SILAR) technique to form Bi2O3/TiO2 nanostructure by the two cycles. The obtained Bi2O3/TiO2 films are consisted of a well-ordered and uniform porous structure with an average pore diameter of about 100-200 nm containing homogeneously dispersed Bi2O3 nanoparticles of similar to 5 nm diameter. Moreover, the resultant composites present excellent photocatalytic performance toward methyl blue (MB) degradation under UV and visible light irradiation, which could be mainly ascribed to the enhanced light adsorption capacity of unique composite structure and the formation of p-n heterojunctions in the porous Bi2O3/TiO2 films. This research is helpful to design and construct the highly efficient heterogeneous semiconductor photocatalysts.