Zhaojian Xu

2D Ruddlesden–Popper metal‐halide perovskites exhibit structural diversity due to a variety of choices of organic ligands. Incorporating bifunctional ligands in such materials is particularly intriguing since it can result in novel electronic properties and functions. However, an in‐depth understanding of the effects of bifunctional ligands on perovskite structures and, consequently, their electronic and excitonic properties, is still lacking. Here, n = 1 2D perovskites built with organic ligands containing ─CN, ─OH, ─COOH, ─phenyl (Ph), and ─CH 3 functional groups are investigated using ultraviolet and inverse photoemission spectroscopies, density functional theory calculations, and tight‐binding model analyses. The experimentally determined electronic gaps of the ─CN, ─COOH, ─Ph, and ─CH 3 based perovskites exhibit a strong correlation with the in‐plane Pb─I─Pb bond angle, while the ─OH based perovskite deviates from the linear trend. Based on the band structure calculations, this anomaly is attributed to the out‐of‐plane dispersion, caused predominantly by significant interlayer electronic coupling that is present in ─OH based perovskites. These results highlight the complex and diverse impacts of organic ligands on electronic properties, especially in terms of the involvement of strong interlayer electronic coupling. The impact of the bifunctional ligands on the evolution of the exciton binding energy is also addressed.