Hydrogen production by water splitting energized by biomass sugars is one of the most promising technologies for distributed green H2 production. Direct H2 generation from NADPH, catalysed by an NADPH‐dependent, soluble NiFe‐hydrogenase (SH1) is thermodynamically unfavourable, resulting in slow volumetric productivity. We designed the biomimetic electron transport chain from NADPH to H2 by the introduction of an oxygen‐insensitive electron mediator benzyl viologen (BV) and an enzyme (NADPH rubredoxin oxidoreductase, NROR), catalysing electron transport between NADPH and BV. The H2 generation rates using this biomimetic chain increased by approximately five‐fold compared to those catalysed only by SH1. The peak volumetric H2 productivity via the in vitro enzymatic pathway comprised of hyperthermophilic glucose 6‐phosphate dehydrogenase, 6‐phosphogluconolactonase, and 6‐phosphogluconate dehydrogenase, NROR, and SH1 was 310 mmol H2/L h−1, the highest rate yet reported. The concept of biomimetic electron transport chains could be applied to both in vitro and in vivo H2 production biosystems and artificial photosynthesis. Sugar rush: A biomimetic electron‐transport chain from NADPH to an electron mediator benzyl viologen catalysed by NADPH rubredoxin oxidoreductase to H2 catalysed by NiFe‐hydrogenase was constructed in vitro. The highest volumetric H2 productivity from glucose 6‐phosphate was 310 mmol H2/L h−1, which was the fastest biological H2 formation rate from sugars yet reported.