Barium tantalum oxynitride (BaTaO2N) with an absorption edge of ca. 660 nm is one of the most promising photocatalysts for solar water splitting, and is usually synthesized by nitriding a mixture of Ba and Ta-containing compounds with a Ba/Ta molar ratio of unity under ammonia flow at high temperature, usually causing a high density of defect sites. Herein, we introduce a novel synthesis method for BaTaO2N (BTON) by employing Ba-rich LiBa4Ta3O12, prepared by a flux method, as a precursor of nitridation. As a comparison, BaTaOx was prepared by conventional solid state reaction and used as the precursor. The as-nitrided samples were correspondingly denoted as BTON-Flux and BTON-SSR. It was found that well-crystallized BTON oxynitride can be similarly obtained by both methods, but the BTON-Flux sample exhibits significantly decreased defect density and enhanced surface area relative to the BTON-SSR sample. As a result of their structural differences, the photocatalytic water splitting performance of the BTON-Flux sample, regardless of the H2-evolving half reaction in the presence of methanol or Z-scheme overall water splitting, is much better than that of BTON-SSR. This study may open up a novel strategy for preparing oxynitride photocatalyst with decreased defect density for the promotion of solar water splitting.