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Abstract Fluorescent proteins (FPs) have recently emerged as a serious contender for realizing ultralow threshold room temperature exciton–polariton condensation and lasing. This contribution investigates the thermalization of FP microcavity exciton–polaritons upon optical pumping under ambient conditions. Polariton cooling is realized using a new FP molecule, called mScarlet, coupled strongly to the optical modes in a Fabry–Pérot cavity. Interestingly, at the threshold excitation energy (fluence) of ≈9 nJ per pulse (15.6 mJ cm⁻²), an effective temperature is observed,T_eff ≈ 350 ± 35 K close to the lattice temperature indicative of strongly thermalized exciton–polaritons at equilibrium. This efficient thermalization results from the interplay of radiative pumping facilitated by the energetics of the lower polariton branch and the cavityQ‐factor. Direct evidence for dramatic switching from an equilibrium state into a metastable state is observed for the organic cavity polariton device at room temperature via deviation from the Maxwell–Boltzmann statistics atk_‖ = 0 above the threshold. Thermalized polariton gases in organic systems at equilibrium hold substantial promise for designing room temperature polaritonic circuits, switches, and lattices for analog simulation.