Electrosynthesis of value-added chemicals, directly from CO2, could foster achievement of carbon neutral through an alternative electrical approach to the energy-intensive thermochemical industry for carbon utilization. Progress in this area, based on electrogeneration of multicarbon products through CO2 electroreduction, however, lags far behind that for C1 products. Reaction routes are complicated and kinetics are slow with scale up to the high levels required for commercialization, posing significant problems. In this review, we identify and summarize state-of-art progress in multicarbon synthesis with a multiscale perspective and discuss current hurdles to be resolved for multicarbon generation from CO2 reduction including atomistic mechanisms, nanoscale electrocatalysts, microscale electrodes, and macroscale electrolyzers with guidelines for future research. The review ends with a cross-scale perspective that links discrepancies between different approaches with extensions to performance and stability issues that arise from extensions to an industrial environment.