The conversion of the alkali‐treated intergrowth germanosilicate CIT‐13 into the single‐crystalline high‐silica ECNU‐21 (named after East China Normal University) zeolite, with a novel topology and a highly crystalline zeolite framework, has been realized through a creative top‐down strategy involving a mild alkaline‐induced multistep process consisting of structural degradation and reconstruction. Instead of acid treatment, hydrolysis in aqueous ammonia solution not only readily cleaved the chemically weak Ge(Si)−O−Ge bonds located within the interlayer double four ring (D4R) units of CIT‐13, but also cleaved the metastable Si−O−Si bonds therein. This led to extensive removal of the D4R units, and also generated silanol groups on adjacent silica‐rich layers, which then condensed to form a novel daughter structure upon calcination. Individual oxygen bridges in the reassembled ECNU‐21 replaced the germanium‐rich D4R units in CIT‐13, thereby eliminating the original intergrowth phenomenon along the b axis. With an ordered crystalline structure of 10‐ring (R) channels as well as suitable germanium‐related Lewis acid sites, ECNU‐21 serves as a stable solid Lewis acid catalyst for the shape‐selective hydration of ethylene oxide (EO) to ethylene glycol (EG) at greatly reduced H2O/EO ratios and reaction temperature in comparison with the noncatalytic industrial process.