As atmospheric CO₂ levels steadily rise, more effective carbon mitigation methods are needed to capture and convert CO₂. Microbial electrosynthesis (MES) is a hybrid electrochemical system in which electro-autotrophic microorganisms utilize electrons from a cathode to convert CO₂ into multi-carbon compounds. This review provides a mechanistic overview of current advancements in MES, emphasizing electron transfer pathways, biocathode architecture, CO₂ mass transfer limitations, and essential techno-economic factors. The inherently poor solubility of CO₂ in water is a primary rate-limiting factor, inhibiting carbon transfer to the Wood-Ljungdahl pathway. Strategies such as gas diffusion electrodes (GDE), biofilm-enhancing surfactants, and pH gradient operation have demonstrated significant improvement in CO2 availability and electron uptake. Advances in 3D nanostructure cathodes, including carbon nanotube-modified carbon felt and metal oxide composites, have achieved good production rates. Techno-economic analysis of acetate production via MES remain constrained by high capital expenditure (CAPEX ≈ 5059 €/tonne product) and the energy burden associated with multi-electron products such as ethanol. Integration of MES with CO₂-rich industrial exhaust streams, renewable power inputs, and metabolic engineering of an electrotrophic framework is expected to reduce operational cost and to improve product selectivity. The review highlights future priorities including advanced kinetic modeling, improved electrode-microbe coupling, and reactor designs that decouple mass transfer from bio-catalytic limitations to accelerate MES towards scalable, carbon-negative bio-manufacturing. Overall, this review delineates the scientific, engineering, and economic levels that must be optimized to transition MES from laboratory systems to commercially viable CO₂ valorization technologies.