White-light broadband emission in the visible range from the low-dimensional halide perovskites is commonly attributed to structural distortions in lead bromide octahedra. In this paper, we report Dion–Jacobson-phase two-dimensional (2D) lead bromide perovskites based on short aromatic diammonium cations, p-phenylene diammonium (pPDA), m-phenylene diammonium (mPDA), and two 1D compounds templated by o-phenylene diammonium (oPDA). All of the compounds exhibit white-light emission. Single-crystal X-ray diffraction analysis reveals that the distortion of the Pb octahedra is influenced by the stereochemistry of the cations and their interactions with the perovskite layers. Solid-state ¹H and ²⁰⁷Pb NMR spectroscopy analysis further confirms this trend, whereby different ¹H and ²⁰⁷Pb chemical shifts are observed for the pPDA and mPDA spacer cations, indicating different hydrogen-bonding interactions and octahedral distortions. Owing to the octahedral distortion, 2D (mPDA)PbBr₄ compounds exhibit broader white-light emission than 2D (pPDA)PbBr₄. Density functional theory calculations suggest that (pPDA)PbBr₄ and (mPDA)PbBr₄ are direct-band-gap semiconductors, and they exhibit larger electronic band gaps and effective masses than the Ruddlesden–Popper-phase (BA)₂PbBr₄. Among the films of these compounds, 2D (mPDA)PbBr₄ shows the best stability, which is attributed to stronger hydrogen-bonding interactions in the material.