Dion–Jacobson (DJ) phase halide perovskites have attracted extensive attention in photovoltaic devices due to their significantly enhanced stability when compared with conventional 3D analogs. However, fundamental questions concerning the quantum well (QW) barrier thicknesses, which are critical to design efficient DJ phase perovskite photovoltaics, remain unknown. Herein, it is unambiguously demonstrated that QW barrier thickness, depending on bulky organic ammonium spacers with different chain lengths, such as 1.3‐propanediamine (PDA), 1.4‐butanediamine (BDA), 1.5‐pentamethylenediamine (PeDA), and 1.6‐hexamethylenediamine (HDA), allows the control of orientation and QW distribution. The DJ phase perovskites based on PDA and BDA have suitable QW barrier thicknesses, which exhibit excellent orientation and more uniform QW distribution, allowing a smooth bandgap transition that leads to longer carrier diffusion length, higher charge mobility, and lower defect density. Conversely, PeDA and HDA, with thicker QW barriers, result in lower orientation and multiple DJ perovskite phases. DJ phase perovskite photovoltaic devices based on PDA and BDA show significantly improved power conversion efficiencies (PCEs) of 14.16% and 16.38% compared with PCEs of 12.95% and 10.55% for PeDA and HDA analogs, respectively.