Perovskite films with different particle sizes and PbI2 contents were prepared by using a controlled single or sequential method. By means of temperature-dependent fluorescence spectroscopy, the energetic distribution of intrinsic intragap trap states in perovskite was quantitatively determined, and the radiative charge recombinations through the band edge and via trap states were studied. Furthermore, a series of thermodynamic parameters, such as the demarcation energy between radiative and nonradiative recombination regions, de-trapping activation energy, and characteristic temperature, were extracted based on which of the possible radiative and nonradiative recombination mechanisms were proposed. In addition, the correlation between the morphology of the perovskite films, the PbI2 content, and the energetic distribution of the trap states was investigated. Finally, we discuss the structure-function relationship of perovskite films prepared by different methods.