Abstractmagnified imageA series of novel gemini dicationic acidic ionic liquids (GDAILs), compounds 1–3 carrying two SO3H groups at the cation moieties and having anions of the type CF3SO$\rm{ _3^ - }$, were synthesized in good yields (Scheme 1). Some physicochemical properties of 1–3 were determined; due to their unique structures, these novel GDAILs showed noticeable hydrophilic properties and strong acidities (Table 1). Beckmann rearrangements of oximes catalyzed by 1, 2, or 3/zinc chloride (GDAIL/ZnCl2) were investigated (Scheme 2); the corresponding amides were formed in up to 99% yield in the presence of 5 mol‐% of GDAIL/ZnCl2 catalyst under optimized conditions (Tables 2 and 3). The peculiar solubilities of 1–3 made the separation of the catalysts from the products very facile, and the catalytic system could be recycled and reused for three times.