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Despite recent interest in lead-free Sn iodide perovskite (ASnI3) solar cells, the role of mixed A-site cations is yet to be fully understood. Here, we report the effect of the ternary mixing of organic A-site cations (guanidium, GA; formamidinium, FA; and phenylethylamine, PEA) on the solar cell performance and charge carrier dynamics that are evaluated using time-resolved microwave conductivity (TRMC). (GAxFA1-x)0.9PEA0.1SnI3 exhibits the maximum power conversion efficiency (PCE) of 7.90% at x = 0.15 and a drastic decrease with increasing GA content. Notably, our TRMC measurements of ASnI3 with/without a hole transport layer reveal the same trend with the devices. From the analyses, we suggest that a variation of electron mobility affected by the location of the GA cation in the grains significantly impacts the PCE. Our work sheds light on the role of mixed A-site cations and directs a route toward the further development of Sn perovskite solar cells.