Hydrogen production from water splitting through electrocatalytic or photoelectrochemical route shows great potential for renewable energy conversion. Herein, the plasmon-enhanced photoelectrical nanocatalysts (NCs) have been successfully developed by Au nanoparticle-decorated Bi2Se3 nanoflowers (Au@Bi2Se3 NFs) as catalysts for hydrogen evolution reaction (HER), leading to a more than 3-fold increase of current under excitation of Au localized surface plasmon resonance (LSPR) and affording a markedly decreased overpotential of 375 mV at a current density of 10 mA cm(-2). The HER enhancement can be largely attributed to effective electron-charge separation and the increase of carrier density in Bi2Se3 induced by the injection of hot electrons of Au nanoparticles. Meanwhile, Bi2Se3 nanoflowers (NFs), a kind of topological insulators, possess gapless edges on boundary and show metallic character on surface, providing a path for the flow of electrons in the electrocatalytic system. This study opens up a new avenue towards the design of higher energy conversion catalytic water splitting systems with the assistance of light energy, which could increase of HER catalysis efficiency by plasmonic excitation. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.