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Herein we report an efficient, simple and green synthesis of novel types of α-hydroxyphosphonates bearing a nitrile group, from the reaction of γ-ketonitriles with dialkyl phosphites in the presence of magnesium oxide as solid support, under solvent-free conditions. All the title compounds were screened for their antioxidant activity by 1,1-diphenyl-2- picrylhydrazyl (DPPH), hydroxyl radical, reducing power and ferrous ion chelating (FIC) methods and they showed significant antioxidant activity.