A series of metal chalcogenides, LiBa(2)M(III)Q(4) (M-III = Al, Ga, In; Q = S, Se), have been successfully obtained by the sealed-tube method. LiBa(2)M(III)Q(4), undergoes a special structural transformation from the P2(1)/m (LiBa(2)AlQ(4) and LiBa2GaS4) to the P2(1)/n (LiBa(2)InQ(4)) space group, which leads to disparities in electronic states, birefringence, and band gaps. Their structures feature the same zigzag [LiM(III)Q(4)](4-) layers consisting of corner-shared LiQ(4) and M(III)Q(4) tetrahedra. The Ba atoms serve to bridge the [LiM(III)Q(4)](4-) layers. The structural comparisons show that the radii of M-III in and the coordination environments of the Ba atoms (BaQ(7) vs BaQ(8)) cooperatively affect the structural transition from simple mirror m to diagonal glide n in LiBa(2)M(III)Q(4). In addition, a statistical analysis uncovers that the M-III/Ba atomic ratio also plays an important role in regulating the structural transition in Ba- and M-III-based chalcogenides.