Hybrid perovskites are promising optoelectronic materials with its attractive optical and electronical properties. Understanding and controlling the intrinsic properties of this material is important for solving the unsettled questions and advancing the performance of the diverse optoelectronic applications. Determining the excitonic behavior is still unexplored despite being able to predict the optoelectronic properties in semiconductors. At this point, we focused on the investigation of CH₃NH₃PbCl₃ perovskite single crystals which are considered an ideal form without having interfacial effects. We verified the structural properties by using the temperature dependence photoluminescence and transmission spectra. We observed the unusual excitonic behaviors near band edge region through the comparing both. In addition, we determined the surface potential distribution with/without the external light source via Kelvin probe force microscopy. Depending on the various light source, we presented the electronic band structures of perovskite crystal which reveal the semiconducting nature of the materials by consolidating the result values of the band gap energy, the work function, and surface photovoltage. We could suggest the identified perovskite structure and possibility to apply to many optoelectronic devices.