Probing local emission properties of organic-inorganic lead halide perovskite material can provide evidence regarding the photovoltaic performance of perovskite solar cells. Herein, cathodoluminescence, which has the potential to resolve emission characteristics in the nanoregime, has been exploited to carry out temperature-dependent studies on individual well-faceted CH3NH3PbI3-xBrx perovskite single crystals. The spatial distribution of emission recorded at 4 and 300 K reveals that the periphery of the perovskite crystals radiates predominantly, which establishes that such an unusual emission characteristic is independent of the crystallographic phase of CH3NH3PbI3-xBrx crystals. Investigation based on scanning transmission electron microscopy coupled with energy dispersive X-ray spectroscopy deduces that the asymmetric cathodoluminescence is associated with the nonhomogeneous distribution of methylammonium cations in CH3NH3PbI3-xBrx single crystals. These results emphasize the unraveling of a correlation between the composition and spectroscopic properties of perovskite crystals in the nanoregime, which eventually can influence the overall photovoltaic performance of the devices based on them.