Abstract A fragment‐reassembly strategy was applied to the construction of 1,4‐dihydropyridines and phosphorus‐substituted 1,4‐dihydropyridines under catalytic radical cation salt‐induced C(sp)3H functionalization of glycine derivatives. Mechanistic studies show that domino C(sp)3H bond oxidation and CN bond cleavage reactions are involved. magnified image