Electrolyte conductivity contributes to the efficiency of devices for electrochemical conversion of carbon dioxide (CO2) into useful chemicals, but the effect of the dissolution of CO2 gas on conductivity has received little attention. Here, we report a joint experimental-theoretical study of the properties of acetonitrile-based CO2-expanded electrolytes (CXEs) that contain high concentrations of CO2 (up to 12 M), achieved by CO2 pressurization. Cyclic voltammetry data and paired simulations show that high concentrations of dissolved CO2 do not impede the kinetics of outer-sphere electron transfer but decrease the solution conductivity at higher pressures. In contrast with conventional behaviors, Jones reactor-based measurements of conductivity show a nonmonotonic dependence on CO2 pressure: a plateau region of constant conductivity up to ca. 4 M CO2 and a region showing reduced conductivity at higher [CO2]. Molecular dynamics simulations reveal that while the intrinsic ionic strength decreases as [CO2] increases, there is a concomitant increase in ionic mobility upon CO2 addition that contributes to stable solution conductivities up to 4 M CO2. Taken together, these results shed light on the mechanisms underpinning electrolyte conductivity in the presence of CO2 and reveal that the dissolution of CO2, although nonpolar by nature, can be leveraged to improve mass transport rates, a result of fundamental and practical significance that could impact the design of next-generation systems for CO2 conversion. Additionally, these results show that conditions in which ample CO2 is available at the electrode surface are achievable without sacrificing the conductivity needed to reach high electrocatalytic currents.