Advanced two-dimensional (2D) ultrathin nanomaterials’ unique structural and electronic properties and their applications in the photo-, photoelectro-, and electro-catalysis fields present timely topics related to the development of sustainable energy. This critical review briefly summarizes the state-of-the-art progress on 2D ultrathin nanomaterials. In this mini review, we started with the synthesis of 2D ultrathin nanomaterials. Then, various strategies for tailoring the electronic and configuration structures of these nanomaterials in the new energy catalysis field are surveyed, where the emphasis is mainly on structure-activity relationships. The advancements of versatile 2D ultrathin nanomaterials in the fields of hydrogen evolution, carbon dioxide conversion, and dinitrogen fixation for sustainable energy were also discussed. Finally, the existing challenges and future research directions in this promising field are presented.