The increasing concentrations of greenhouse gases into the atmosphere call for urgent measures to use non-fossil feedstock for fuels and chemicals. Synthesis gas (or syngas) is a mixture of three gases: hydrogen (H2), carbon monoxide (CO), and carbon dioxide (CO2). Syngas already is widely used as a non-fossil fuel and a building block for a variety of chemicals using the Fischer-Tropsch process. Recently, syngas fermentation has attracted attention as a more sustainable way for the conversion of syngas to chemicals, since its biocatalysts are self-generating, are resilient, and can utilize a wide range of syngas compositions. However, syngas fermentation has technical and economic limitations. This dissertation, by contributing to the understanding of syngas fermentation, helps to overcome the limitations. A bibliometric analysis showed the topic’s landscape and identified that mass transfer is the biggest challenge for the process. One means to improve syngas mass transfer is to use the membrane biofilm reactor, or MBfR, to deliver syngas to the microorganisms. MBfR experiments delivering pure H2 demonstrated that the H2:IC ratio (IC is inorganic carbon) controlled the overall production rate of organic compounds and their carbon-chain length. Organic chemicals up to eight carbons could be produced with a high H2:IC ratio. A novel asymmetric membrane dramatically improved mass transfer rates for all syngas components, and its low selectivity among them made it ideal for high-rate syngas fermentation. MBfR experiments using syngas and the asymmetric membrane, as well as a conventional symmetric membrane, confirmed that the key parameter for generating long-chain products was a high H2:IC ratio. The fast mass transfer rate of the asymmetric membrane allowed a very high areal production rate of acetate: 253 g.m-2.d-1, the highest reported to date. Since the membrane delivered H2 and C from the syngas feed, the relatively low selectivity of the asymmetric membrane favored acetogenesis over microbial chain elongation. A techno-economic analysis of the MBfR showed that the cost to produce acetate was less than its market price. All results presented in this dissertation support the potential of syngas fermentation using the MBfR as a means to produce commodity chemicals and biofuels from syngas.