The coordination states of aluminium,boron in Na2O-Al2O3-BaO3-P2O5 glasses have been studied by means of Raman spectroscopy. The study shows that when boron,aluminium ions coexist in phosphate glasses, it is possible that boron iong form BO4 tetrahedra prior to aluminium ions, with the former having three or four coordinations,the latter having four or six.