The first synthesis of single phased gallium oxysulfide (b-Ga 2 O 3Àx S x ), gallium oxyselenide (b-Ga 2 O 3Àx Se x ) and gallium oxytelluride (b-Ga 2 O 3Àx Te x ) was actualized. The luminescence intensity of Ga 2 O 2:95 S 0:05 is the highest of the above samples, i.e., it shows fourfold enhancement in comparison with that of Ga 2 O 3 . Furthermore, the intensity of Ga 2 O 2:95 Se 0:05 and Ga 2 O 2:95 Te 0:05 is lower than that of Ga 2 O 3 . Those trends are attributed to the two effects of the electron delocalization and the distance between donor and acceptor. The spectra of VIb-ion-doped samples, i.e., Ga 2 O 2:95 S 0:05 , Ga 2 O 2:95 Se 0:05 and Ga 2 O 2:95 Te 0:05 , show a redshift behavior by 10 nm in comparison with that of Ga 2 O 3 . The redshift behavior can be explained by the Nephelauxetic effect. Our results showed a means of achieving emission intensity enhancement through changing the cation environment in b-Ga 2 O 3 .