Two-dimensional (2D) halide perovskites have several distinct structural classes and exhibit great tunability, stability, and high potential for photovoltaic applications. Here, we report a new series of hybrid 2D perovskites in the Dion–Jacobson (DJ) class based on aromatic m-phenylenediammonium (mPDA) dications. The crystal structures of the DJ perovskite materials (mPDA)MAn–1PbnI3n+1 (n = 1–3) were solved and refined using single-crystal X-ray crystallography. The results indicate a short I···I interlayer distance of 4.00–4.04 Å for the (mPDA)MAn–1PbnI3n+1 (n = 2 and 3) structures, which is the shortest among DJ perovskites. However, Pb–I–Pb angles are as small as 158–160°, reflecting the large distortion of the inorganic framework, which results in larger band gaps for these materials than those in other DJ analogues. Density functional theory calculations suggest appreciable dispersion in the stacking direction, unlike the band structures of the Ruddlesden–Popper phases, which exhibit flat bands along the stacking direction. This is a consequence of the short interlayer I···I distances that can lead to interlayer electronic coupling across the layers. The solution-deposited films (nominal (mPDA)MAn–1PbnI3n+1 compositions of n = 1–6) reveal improved surface coverage with increasing nominal n value with the higher n films being composed of a mixture of n = 1 and bulk three-dimensional MAPbI3 perovskites. The films made from solutions of these materials behave differently from those of other 2D iodide perovskites, and their solar cells have a mixture of n = 1 DJ and MAPbI3 as light-absorbing semiconductors.