An efficient tandem reaction of imidamides and N-hydroxycarbamates has been developed. Valuable 2-alkylbenzimidazoles could be easily obtained in up to 97% yield for more than 20 examples. The products would further streamline the synthesis of molecules, which are essential building blocks in organic synthesis and drug discovery. This protocol features high regioselectivity, efficiency, good tolerance of functional groups, and mild reaction conditions.