Organic-inorganic hybrid perovskite nanocrystals have attracted a lot of attention owing to their excellent optical properties such as high absorption coefficient, high diffusion length, and photoluminescence quantum yield in optoelectronic applications. Despite the many advantages of optoelectronic materials, understanding on how these materials interact with their environments is still lacking. In this study, the fluorescence properties of methylammonium lead bromide (CH3NH3PbBr3, MAPbBr3) nanoparticles are investigated for the detection of volatile organic compounds (VOCs) and aliphatic amines (monoethylamine, diethylamine, and trimethylamine). In particular, colloidal MAPbBr3 nanoparticles demonstrate a high selectivity in response to diethylamine, in which a significant photoluminescence (PL) quenching (~ 100%) is observed at a concentration of 100 ppm. This selectivity to the aliphatic amines may originate from the relative size of the amine molecules that must be accommodated in the perovskite crystals structure with a narrow range of tolerance factor. Sensitive PL response of MAPbBr3 nanocrystals suggests a simple and effective strategy for colorimetric and fluorescence sensing of aliphatic amines in organic solution phase.