Lead halide perovskites (LHPs) have a diverse compositional range owing to various employable A-and X-site ions. However, the effect of underlying charge transport layer (CTLs) on the charge transport properties in the composition-varied LHPs remains uncertain. Herein, we employed optical spectroscopies and time-resolved microwave conductivity (TRMC) to investigate the dependence of the optical and photoconductive properties of various A-site (formamidinium: FA, methylammonium: MA, Cs) and X-site (Br, I) compositions of LHPs with different underlying CTLs. Intriguingly, it was found that tricationic FAMACs-based LHPs showed more efficient charge separation than bicationic FACs-and FAMA-based ones in a regular structure. Conversely, FACs-based LHPs showed more efficient charge separation than the others in an inverted structure, as evidenced by the prolonged lifetime of TRMC decays. In alignment with these TRMC results, FAMACs exhibited higher device performance in a regular structure than inverted structure. Whereas, FACs showed superior performance in an inverted structure. Hence, our study revealed that the optimal device structure is compositionally dependent on the charge carrier dynamics.