The development of high-efficiency heterojunction photocatalysts has been recognized as an effective approach to facilitate photocatalytic CO 2 reduction. In this research, we successfully synthesized a novel multiflower-like ReS 2 /NiAl-LDH heterojunction through a hydrothermal method. Remarkably, when exposed to visiblelight irradiation, 2-ReS 2 /NiAl-LDH demonstrated an exceptional CO production rate of 272.26 μmol•g −1 •h −1 , which was 4.0 and 10.8 times higher than that of pristine NiAl-LDH and ReS 2 . The intertwined structure of ReS 2 and NiAl-LDH promoted the efficient transfer and separation of photogenerated carriers, thereby significantly enhancing the photocatalytic CO 2 reduction capabilities of the ReS 2 /NiAl-LDH. Furthermore, the carrier transfer pathway for the 2-ReS 2 /NiAl-LDH heterojunction was elucidated, suggesting a type II scheme mechanism, as evidenced by photochemical deposition experiments. The findings of this study offer valuable insights and pave the way for future research in the design and construction of LDH-based and ReS 2 -based heterojunctions for efficient photocatalytic CO 2 reduction.