The field of 2D materials has advanced significantly with the emergence of MBenes, a new material derived from the MAX phases family, a novel class of materials that originates from the MAX phases family. Herein, this article explores the unique characteristics and morphological variations of MBenes, offering a comprehensive overview of their structural evolution. First, the discussion explores the evolutionary period of 2D MBenes associated with the several techniques for synthesizing, modifying, and characterizing MBenes to tailor their structure and enhance their functionality. The focus then shifts to the defect chemistry of MBenes, electronic, catalytic, and photothermal properties which play a crucial role in designing multifunctional solar‐driven hybrid systems. Second, the recent advancements and potentials of 2D MBenes in solar‐driven hybrid systems e.g. photo‐electro catalysis, hybrid solar evaporators for freshwater and thermoelectric generators, and phototherapy, emphasizing their crucial significance in tackling energy and environmental issues, are explored. The study further explores the fundamental principles that regulate the improved photocatalytic and photothermal characteristics of MBenes, highlighting their promise for effective utilization of solar energy and remediation of the environment. The study also thoroughly assesses MBenes' scalability, stability, and cost effectiveness in solar‐driven systems. Current insights and future directions allow researchers to utilize MBenes for sustainable and varied applications. This review regarding MBenes will be valuable to early researchers intrigued with synthesizing and utilizing 2D materials for solar‐powered water‐energy‐fuel and phototherapy systems.