<p>Microbial electrosynthesis (MES) is at the forefront of sustainable biotechnologies, leveraging the unique abilities of microorganisms to interact with and facilitate electrochemical reactions at the electrode–microbe interface. Scientific investigations are ongoing to implement MES for CO₂ sequestration to mitigate climate change. Utilizing electrogenic microorganisms as biocatalysts for MES, CO₂ can be transformed, serving as an energy or electron donor, into a variety of carbon products derived from waste or pollution, thereby accounting for carbon–neutral practices and addressing a range of ongoing environmental problems. Operational strategies such as reactor hybridization and optimized biocathode design play a crucial role in enhancing electrosynthetic productivity while reducing cathode material requirements and overall operational costs. This review aims to highlight the versatility of MES in producing a range of value-added chemicals, biofuels, and biochemicals, thereby promoting more sustainable industrial practices. There are integration and cyclic pathways for connections between MES and other systems, such as carbon capture and wastewater treatment. We review current developments in microbial engineering, electrode materials, and process connections that will be necessary for addressing some of these challenges in transitioning MES from a promising lab-scale technology to commercial readiness.</p>