The oxynitrides with composition A1-xBx(OyNz) (A: Nb and Ta, B: Al) were studied in preparation through citrate route and NH3 nitridation. In the case of Nb, the product of x = 0.5 prepared at 1000 °C was a new compound of a = 0.435 nm with rock salt structure. In this structure, Al and Nb atoms were distributed randomly in the cation sites. Anion sites were also randomly occupied by oxide and nitride ions with some amount of vacancy. The chemical composition was represented as Nb0.56Al0.44O0.38N0.37□0.25 from Rietveld refinement and oxygen/ nitrogen measurement. In the case of Ta, monoclinic Ta3N5 crystallized with a small amount of Ta4N5 impurity at x = 0.5. Aluminum compound was co-present as amorphous impurity.