Bi2WO6:Eu3+ samples were prepared by mechanically activated metathesis reaction and subsequent annealing at different temperatures of the as-prepared precursor. X-ray, TEM, Raman, IR, diffuse reflectance and luminescence studies of the prepared samples are presented. It was found that variation of the particle size have significant impact on phonon and emission properties of this material. It was observed that intensity of some Raman and IR bands significantly decreases and the bandwidth of Raman, IR and Eu3+ emission lines significantly increases with decreasing particles size. Moreover, it was observed that intensity ratios I((5)D0-(7)F2)/I((5)D0-(7)F1) and I(5D0_(7)F0)/I((5)D0-(7)F1) increase with decreasing particle size. The observed changes were attributed to phonon confinement effect, decrease in the orthorhombic distortion of the unit cell and concentration increase of surface defects.