The stereochemical expression of the 6s2 lone pair on the lead atom has a significant impact on the crystal structures and physical properties of lead halide perovskites. Two-dimensional (2D) lead bromide perovskites often exhibit a broadband emission, yet the structural origin of the broadband emission has been under debate. Here, we report the synthesis and characterization of a 2D lead bromide hybrid (4-chlorophenylammonium)2PbBr4 that consists of a combination of the octahedral unit PbBr6 and the rarely observed capped octahedral unit PbBr7 through corner-sharing and edge-sharing linkages. The seven-coordination geometry indicates a strong stereo-active lone pair on the Pb2+ cation. By comparing this structure with two representative 2D perovskites, (benzylammonium)2PbBr4 and (4-aminotetrahydropyran)2PbBr4, we establish how the lone pair expression affects the local coordination geometry of the Pb2+ cation and the resulting optical and electronic properties. As the Pb-Br bond length increases, the lone pair expression leads to off-centering displacement of Pb2+ within the octahedra and then the formation of seven-coordination capped octahedra. Density functional theory calculations indicate that the off-centering distorted octahedra and capped octahedra are due to the asymmetric distribution of the Pb electrons that have both s and p orbital characteristics. Spectroscopic studies show the photoluminescence spectra evolving from narrowband emission to broadband emission with increasing LPE, as well as softer and more anharmonic lattice vibrations that facilitate exciton self-trapping. Our results demonstrate that lone pairs could be a powerful design rule for developing light emitting materials.