Rh nanospheres anchored TaON Ta2O5 with shell-core structure was synthesized from in situ Rh3+-doped Ta2O5 by one-step high-temperature ammonolysis, which exhibited efficient visible light photoactivity for H-2-evolution (39.41 mu mol.g(-1).h(-1)), much higher than unmodified Ta3N5 Ta2O5 (21.75 mu.mol.g(-1).h(-1)). Rh-modifying inhibited the phase transformation from TaON to Ta3N5 during the nitridation process, and increased the specific surface area and active sites, and extended the optical absorption throughout visible light region due to localized surface plasmon resonance (LSPR) effect. Relative intensities of peaks at 827 cm(-1) for Ta-O bonds increased with increasing Rh-modifying amounts, which was beneficial to improving the stability. Notably, constructing novel Rh/TaON/Ta2O5 hetero-junctions including a Rh/TaON Schottky junction and an n-n TaON/Ta2O5 mutant hetero-junction facilitated photogenerated carriers directed transfer from inner to surface active sites, and decreased travel distance of charge carriers, and formed built-in electric fields to accelerating charge separation. Synergetic effects of the enhanced photocatalytic H-2-evolution activity were discussed in detail. This work provided a promising strategy to further design and develop efficient and stable Ta-based photocatalysts for solar water splitting. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.