A series of the Sr1.9ZnW1-xMoxO6:0.05Eu3+,0.05Li+ phosphors was synthesized by high-temperature solid-state reaction method. The structure, ultraviolet-visible diffuse reflectance spectra, photoluminescence and decay properties of the phosphors were investigated as a function of the W/Mo ratio. All prepared mixed compounds have a cubic structure. The experimental spectroscopic results show the excitation bands of these phosphors is in the near ultraviolet region; the red-shift of these bands is observed upon increase of the Mo concentration. The strong red and weak orange-red emissions centered at 614 and 595 nm, respectively, were observed, which indicates that Eu3+ occupies the non-centrosymmetric site. Co-doping with Mo can enhance the luminescent intensity and the optimal concentration was determined to be x=0.4. Combination of the first-principles calculations with the experimental spectroscopic measurements confirmed an indirect band gap character for the prepared phosphors and allowed for estimation of their band gap value.