Quadruple cation mixed halide perovskite, GA0.015Cs0.046MA0.152FA0.787Pb(I0.815Br0.185)3, single crystals were grown for the first time using an inverse temperature crystallization process. Solar cell devices in n-i-p stack configuration using thin films of the same materials showed power conversion efficiency above 20%. Complementary time-resolved spectroscopy confirmed that polycrystalline thin films and single crystals identically composed exhibit similar carrier dynamics in the picosecond range. Cooling of excited carriers and bandgap renormalization occur on the same time scale of 200–300 fs. The radiative recombination coefficient (1.2 × 10–9 cm3/s) is comparable to values reported for a GaAs semiconductor. At low excitation density, a long carrier lifetime of 3.2 μs was recorded possibly due to the passivation of recombination centers. This study clarifies discrepancies about the lifetime of hot carriers, the impact of radiative recombination, and the role of recombination centers on solar cell performance. The quadruple cation perovskites displayed short time dynamics with slow recombination of charge carriers.