Electrosynthesis offers a powerful tool for the formation of anion and cation radical intermediates and for driving clean synthetic reactions without the need for additional chemical reagents. Recent advances in microfluidic reactor technologies triggered an opportunity for new microflow electrolysis reactions to be developed for novel and clean electrosynthetic processes. Naturally, two electrodes, anode and cathode, are required in all electrochemical processes and combining the two electrode processes into one "paired" reaction allows waste to be minimised. By decreasing the inter-electrode gap "paired" reactions may be further "coupled" by overlapping diffusion layers. The concept of "coupling" electrode processes is new and in some cases coupled processes in micro-flow cells are possible even in the absence of intentionally added electrolyte. The charged intermediates in the inter-electrode gap act as electrolyte and processes become "self-supported". Hardly any examples of "coupled" paired electrochemical processes are known to date and both "paired" and "coupled" processes are reviewed here. Coupled electrode processes remain a challenge. In future "pairing" and "coupling" electrode processes into more complex reaction sequences will be the key to novel and clean flow-through microreactor processes and to novel chemistry.