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• Ru 0.7 Cu 0.3 /W 18 O 49 Schottky junction is synthesized. • Metallic Ru 0.7 Cu 0.3 exhibits LSPR effects, enhancing AB hydrolysis activity. • The photocatalytic mechanism for H 2 generation is systematically expounded. Photocatalytic hydrogen (H 2) production from ammonia borane (AB) hydrolysis is a promising pathway for generating clean energy. Constructing appropriate heterojunctions represents an efficient strategy for enhancing the catalytic activity. Herein, a Ru 0.7 Cu 0.3 /W 18 O 49 Schottky junction is successfully designed, which greatly enhances transfer and separation of photogenerated charge carriers. Moreover, the metallic Ru 0.7 Cu 0.3 exhibits localized surface plasmon resonance (LSPR), which greatly enhances the light harvesting capability. As expected, the optimized Ru 0.7 Cu 0.3 /W 18 O 49 photocatalyst exhibits a superior visible-light-driven H 2 generation yield of 880 mL min−1 g−1 with excellent stability. The turnover frequency (TOF) value of Ru 0.7 Cu 0.3 /W 18 O 49 was found to be 1.44 times higher under visible light irradiation compared to the dark condition, achieving 133.1 min−1. The present study establishes a pioneering approach for the systematic design of highly efficient and durable heterostructure catalysts. [ABSTRACT FROM AUTHOR]