 2D perovskite films with spacers exhibit a mixture of excitons and free-charge carriers, which can be determined by time-resolved photoluminescence decay, quantum yield, and initial rate of photon emission. The model considers non-interacting populations in separate subvolumes, reproducing unique features such as the anomalous peak of PLQY at intermediate fluences. Effective rates of free carrier recombination and exciton-exciton annihilation are high, with implications for device engineering based on different excited state populations and dynamics. This article was authored by Milan Kaiser, Young Lee, Isabella Legro, and others.