Estimates of the atmospheric concentration of CO2, [CO2]atm, for the “hothouse” climate of the early Eocene climatic optimum (EECO) vary for different proxies. Extensive beds of the mineral nahcolite (NaHCO3) in evaporite deposits of the Green River Formation, Piceance Creek Basin, Colorado, USA, previously established [CO2]atm for the EECO to be >1125 ppm by volume (ppm). Here, we present experimental data that revise the sodium carbonate mineral equilibria as a function of [CO2] and temperature. Co-precipitation of nahcolite and halite (NaCl) now establishes a well-constrained lower [CO2]atm limit of 680 ppm for the EECO. Paleotemperature estimates from leaf fossils and fluid inclusions in halite suggest an upper limit for [CO2]atm in the EECO from the nahcolite proxy of ∼1260 ppm. These data support a causal connection between elevated [CO2]atm and early Eocene global warmth, but at significantly lower [CO2]atm than previously thought, which suggests that ancient climates on Earth may have been more sensitive to a doubling of [CO2]atm than is currently assumed.