The optical band-gap energy of a nanostructured tungsten trioxide film is determined using the photoacoustic spectroscopy method under continuous light excitation. The mechanism of the photoacoustic signal generation is discussed. The band-gap energy is also computed by other methods. The absorption coefficient as well as the band-gap energy of three different crystal structures of tungsten trioxide is calculated by a first-principles Green's function approach using the projector augmented wave method. The theoretical study indicates that the cubic crystal structure shows good agreement with the experimental data.