AbstractCommercialization of Zn‐metal anodes with low cost and high theoretical capacity is hindered by the poor reversibility caused by dendrites growth, side reactions, and the slow Zn2+‐transport and reaction kinetics. Herein, a reversible heterogeneous electrode of Zn‐nanocrystallites/polyvinyl‐phosphonic acrylamide (Zn/PPAm) with fast electrochemical kinetics is designed for the first time: phosphonic acid groups with strong polarity and chelation effect ensure structural reversibility and stability of the three‐dimensional Zn‐storage‐host PPAm network and the Zn/PPAm hybrid; hydrophobic carbon chains suppress side reactions such as hydrogen evolution and corrosion; weak electron‐donating amide groups constitute Zn2+‐transport channels and promote “desolvation” and “solvation” effects of Zn2+ by dragging the PPAm network on the Zn‐metal surface to compress/stretch during Zn plating/stripping, respectively; and the heterostructure and Zn nanocrystallites suppress dendrite growth and enhance electrochemical reactivity, respectively. Thus, the Zn/PPAm electrode shows cycle reversibility of over 6000 h with a hysteresis voltage as low as 31 mV in symmetrical cells and excellent durability and flexibility in fiber‐shaped batteries.