Microbial electrosynthesis (MES) is an emerging biotechnology platform for the conversion of CO2 feedstocks into value-added chemical commodities. In MES, microbial catalysts use the cathode (electrons/ H2) as a sole source of energy for the reduction of CO2. Integrating MES technology with renewable energy sources, such as solar power, to convert CO2 to storable chemicals is an example of a perfect circular economy and a sustainable climate change mitigation strategy. However, many knowledge gaps need to be addressed to scale-up MES as an economically viable chemical production process. Therefore, different in-depth approaches were tested in this dissertation by optimizing the cathode architecture and exploring the saline application to enhance MES performance. A balance between various bio-physicochemical phenomena at the MES cathode, i.e., the three-phase interface between CO2 gas, cathodic-biofilm, and electrolyte, is desirable for efficient microbial electrochemical CO2 capture and utilization. To address this problem, this thesis investigated alternatives to the benchmark carbon-based plane cathode by applying a dual-functioning (cathode as well as a CO2 gas-transfer membrane) electrode architecture on MES performance. High Faradaic efficiencies for CO2 reduction were achieved with this novel cathode architecture. This hollow-fiber electrode architecture was also applied to MES operation in saline conditions (i.e., Saline-MES). Because seawater potentially acts as an endless source of saline electrolyte, and its high electrical conductivity useful to minimize the concentration overpotential losses occurs in MES. However, exploring robust halophilic microbial catalysts with high selectivity towards CO2 reduction to the desired end product(s) is necessary to develop the saline-MES process. Therefore, this thesis investigated natural saline habitats with hyper (Red sea brine pool) and moderate salinity (mangrove and salt marsh sediment) as a source of inoculum. Emphasis was placed on improving new knowledge in the direction of halophilic CO2 reducing communities enrichment using cathode selective pressure in the saline-MES. The fundamental insights demonstrated in this dissertation are useful for further development of MES technology, to bring MES one step closer to full-scale applications, for overcoming the bottlenecks associated with reactor scaling-up related to cathode architecture, strategies for the enrichment of halophilic CO2 reducing microbial communities, and saline-MES process optimization.