A highly enantioselective 1,4-addition reaction of nitroalkenes with diphenyl phosphite was successfully accomplished using a newly developed axially chiral guainidine catalyst. A broad range of nitroalkenes, bearing not only aromatic but also aliphatic substituents, is applicable to the present enantioselective reaction. The method provides an efficient protocol to synthesize enantioenriched beta-amino phosphonate derivatives of biological and pharmaceutical importance.