The potential applications of perovskite manganite R1-xAxMnO3 (R = rare earth element; A = Sr, Ca) thin films have been continuously explored due to their multi-functional properties. In particular, the optimally hole-doped La0.67Ca0.33MnO3 thin film demonstrates a colossal magneto-resistance that is beneficial to the performance of spintronic devices. To understand the effect of R and A ions on the material properties, we systematically measure the resistivity, magnetization, and electronic energy states for three optimally hole-doped R0.67A0.33MnO3 thin films with R = La, Sm and A = Sr, Ca. Various energy parameters are derived based on the X-ray absorption and X-ray photoelectron spectra, including the band gap, the charge frustration energy and the magnetic exchange energy. It is interesting to find that the replacement of La with Sm is more effective than that of Sr with Ca in terms of tuning the electrical property, the Curie temperature, and the band gap. The strain-induced reduction of the O 2p- Mn 3d hybridization and the interplay of R/A site disorder and strain effect are discussed. The results of this study provide useful information for the band design of perovskite oxide films.