State-of-the-art triple cation, mixed halide perovskites are extensively studied in perovskite solar cells, showing very promising performance and stability. However, an in-depth fundamental understanding of how the phase behavior in Cs_0.05FA_0.85MA_0.10Pb(I_0.97Br_0.03)₃ (CsMAFA) affects the optoelectronic properties is still lacking. The refined unit cell parameters a and c in combination with the thermal expansion coefficients derived from X-ray diffraction patterns reveal that CsMAFA undergoes an α–β phase transition at ≈280 K and another transition to the γ-phase at ≈180 K. From the analyses of the electrodeless microwave photoconductivity measurements it is shown that shallow traps only in the γ-phase negatively affect the charge carrier dynamics. Most importantly, CsMAFA exhibits the lowest amount of microstrain in the β-phase at around 240 K, corresponding to the lowest amount of trap density, which translates into the longest charge carrier diffusion length for electrons and holes. Below 200 K a considerable increase in deep trap states is found most likely related to the temperature-induced compressive microstrain leading to a huge imbalance in charge carrier diffusion lengths between electrons and holes. This work provides valuable insight into how temperature-dependent changes in structure affect the charge carrier dynamics in FA-rich perovskites.