Electrocatalysis plays a vital role in energy conversion and storage in modern society. Localized surface plasmon resonance (LSPR) is a highly attractive approach to enhance the electrocatalytic activity and selectivity with solar energy. LSPR excitation can induce the transfer of hot electrons and holes, electromagnetic field enhancement, lattice heating, resonant energy transfer and scattering, in turn boosting a variety of electrocatalytic reactions. Although the LSPR-mediated electrocatalysis has been investigated, the underlying mechanism has not been well explained. Moreover, the efficiency is strongly dependent on the structure and composition of plasmonic metals. In this review, the currently proposed mechanisms for plasmon-mediated electrocatalysis are introduced and the preparation methods to design supported plasmonic nanostructures and related electrodes are summarized. In addition, we focus on the characterization strategies used for verifying and differentiating LSPR mechanisms involved at the electrochemical interface. Following that are highlights of representative examples of direct plasmonic metal-driven and indirect plasmon-enhanced electrocatalytic reactions. Finally, this review concludes with a discussion on the remaining challenges and future opportunities for coupling LSPR with electrocatalysis.