A subtle combination of fundamental and applied organic chemistry toward process intensification is demonstrated for the large‐scale production of bio‐based glycerol carbonate under flow conditions. The direct carbonation of bio‐based glycidol with CO2 is successfully carried out under intensified flow conditions, with Barton’s base as a potent homogeneous organocatalyst. Process metrics for the CO2 coupling step (for the upstream production, output: 3.6 kg day‐1, Space Time Yield (STY): 2.7 kg h‐1 L‐1, Environmental factor (E‐factor): 4.7) outclass previous reports. High conversion and selectivity are achieved in less than 30 s of residence time at pilot scale with a stoichiometric amount of CO2. Supporting DFT computations reveal the unique features of the mechanism in presence of Brønsted bases.