Two‐dimensional materials (2D M) possess unique structural, optical, and electronic properties in comparison with their bulk counterparts. Therefore, they have been demonstrated to be excellent performers for catalysis (especially photocatalysis). Among these 2D catalytic materials, 2D silicon (2D Si) is an emerging subclass, gifted with Si's high abundance, low toxicity, and strong light‐harvesting ability. Endowed with the universal advantages of 2D M including a large surface area, prolific active sites and loading positions for other elements, and ultrathin thickness for the generation of defects and transportation of photogenerated carriers, 2D Si exhibits additionally distinct surface chemistry and metal‐support interactions through geometrical assembly. These features render 2D Si a competitive candidate for (photo)catalysis, drawing burgeoning interest recently.