The emergence of Mo2C- based catalysts in recent years has been favored as promising contender within diverse class MXenes. In terms of rapid development in the photocatalytic application, these intriguing compounds exhibit excellent photocatalytic performance because of their superior optical properties and peculiar structure characteristics. Unfortunately, a systematic review of Mo2C- based catalysts is lacking. In this review, we abstract the implication of structure—property relationship of emerging Mo2C- based MXenes materials and their applications toward the photocatalytic hydrogen evolution reaction (HER). Furthermore, synthetic pathways to prepare high-quality, low cost Mo2C- based MXenes materials and their outcomes for high HER applications are systematically described. Finally, several insights are provided into the prospects and future challenges for the development of highly reactive Mo2C- based MXenes materials, which present large range opportunities in this promising 2D materials for green and clean energy in environmental fields. This review provides a comprehensive scientific guide to the preparation, modification, and photocatalytic HER of MXenes-based materials.