n-type porous silicons are prepared by the electrochemical corrosion method, on which tungsten oxide thin films with different thickness values are sputtered using DC reactive magnetron sputtering. The structures of ordered porous silicons and tungsten oxide thin films are characterized using field emission scanning electron microscope, which show that the pores are pillared and ordered and the thin films cover the porous layer loosely with many pores open to ambient air. The X-ray diffraction characterization indicates that the lattice structure of tungsten oxide thin film is mainly triclinic polycrystalline. The gas-sensing properties at room temperature for both ordered porous silicon and composite structure are studied, which indicate that the latter is much more sensitive to nitrogen dioxide than the former. And there is a critical spurting time of WO3 thin film, which in our case is 10 min. The sensing mechanism of composite structure is discussed and the probable explanation for the improvement of sensitivity to NO2 is the formation of hetero-junctions between the ordered porous silicon layer and the WO3 thin film. In addition, there exists an inversion layer on the surface of the WO3 thin film, which causes the anomalous resistance to change during the gas sensing measurements.