For the first time, novel Ba3−xWO6:xEu3+ (x=0.01, 0.03, 0.05, 0.08, 0.1) nanowire phosphors were synthesized by the conventional solid state method. The X-ray pattern indicates that Ba3WO6 belongs to the cubic system with space group Fm-3m. The photoluminescence (PL) spectra demonstrate that the phosphors emit strong red light centered at 595nm corresponding to 5D0→7F1 transition of Eu3+ ion under CT band excitation. The position of charge transfer (CT) band of Ba2.95WO6:0.05Eu3+ shifts to a lower energy region (red shift) with the increase of annealing temperature. The co-doped effect of alkali-metal ions (Li+, Na+, and K+) on the luminescence behavior of Ba3WO6:Eu3+ has been discussed in this paper. The luminescence properties suggest that the Ba3WO6:Eu3+ phosphor may be a promising candidate in solid-state lighting applications.