The first organocatalytic highly enantioselective reactions of substituted α-cyanoacetates and β-dicarbonyl compounds with azodicarboxylates are reported. In the presence of 0.1−5 mol % of a quinidine-derived alkaloid β-ICD, optically active quaternary hydrazine adducts are obtained in very high yields and with enantioselectivities up to >98% ee. A two-step procedure for the cleavage of the hydrazine N−N bond using SmI2 is also demonstrated.