The higher levels of intra- and inter-octahedral distortion in the structure of 2[PbBr4], relative to 1[PbBr4], results in striking differences in the steady-state photoluminescence (PL) properties of these two materials. At room temperature, the emission of the less-distorted compound 1[PbBr4] features a predominant narrowband, blue emission ranging from 430 to 500 nm, with a broad and unstructured tail.