Abstract A diastereoselective and enantioselective conjugate addition of α‐substituted acyl imidazole to nitroalkene catalyzed by nickel bisoxazoline complex and B(C 6 F 5 ) 3 has been developed. This reaction tolerated a wide range of acyl imidazoles and nitroalkenes, affording a series of conjugate adducts in yields ranging from 38% to 99% with 4:1 to 99:1 dr and 13% to 98% ee. The use of strong Lewis acid B(C 6 F 5 ) 3 as co‐catalyst proved vital to the success of this process. The potential scalability and utility of the current protocol are demonstrated by a reaction on a 3 mmol scale and further transformations of the product. magnified image