Plasmon-enhanced photo/electrocatalysis using hetero-nanostructures has emerged as a promising approach for boosting the efficiency and selectivity of photo/electrocatalytic reactions. Plasmonic nanostructures (PNSs), with their unique properties including localized surface plasmon resonance (LSPR), play a vital role in enhancing photo/electrocatalytic activities. By leveraging LSPR, PNSs can concentrate incident light, facilitate charge separation, and induce surface reactions, leading to improved catalytic performance. In this review, we provide a comprehensive analysis of the current state of knowledge in this field. We discuss the rational design and synthesis of hetero-nanostructures, focusing on the optimization of composition, size, shape, and interface properties. Furthermore, we explore various combinations of plasmonic sources with semiconductors of diverse morphologies to achieve enhanced photocatalytic activity. The reviewed research encompasses applications in water splitting, removal of organic pollutants, CO2 reduction, and energy conversion. We also address the challenges that need to be overcome, including optimization of materials, reproducibility, stability, band alignment, and understanding plasmon–material interactions in hetero-nanostructures. The review of future perspectives includes the integration of multiple functionalities, the exploration of novel plasmonic materials, and the translation of plasmon-enhanced photo/electrocatalysis into practical applications. The combination of plasmonics and nanotechnology can be used to advance green technologies and address pressing global issues.