The optical properties of tungsten trioxide thin films prepared by DC magnetron sputtering, with The origin of peak P2 is more uncertain, but may involve +1 and +2 charged vacancy sites. The PL spectra show several emission bands in the range 2.07 to 3.10 eV in the more sub-stoichiometric, and 2.40 to 3.02 eV in the less sub-stoichiometric films. The low energy emission bands agree well with calculated optical transition energies of oxygen vacancy sites, with dominant contribution from neutral and singly charged vacancies in the less sub-stoichiometric films, and additional contributions from doubly charged vacancy sites in the more sub-stoichiometric films.