This work is devoted to the numerical analysis of the opportunity to obtain a steady generation of electromotive force (EMF) in a two-chamber gas cell exposed to concentrated solar/lamp radiation. For this purpose, we have carried out 2D simulations of the low-pressure photoplasma in the mixtures of sodium atom vapor and different noble gases and their pressures at different values of photoexcitation rate of resonance levels of Na. Herewith plasma chemistry and transfer of charges and radiation in the volume have been taken into account. It has been established that argon is a better candidate to be used as a buffer gas for photoplasma electric converter based on the obtained plasma parameters and commercial aspects. A parametric study has been carried out for the Na–Ar mixture to investigate the effect of increasing homogeneous photoexcitation rate in the small chamber on plasma parameters and obtained EMF. Another parametric study has been conducted to calculate the output current and electric power at a loaded chain. The results show that EMF could be obtained using the photovoltaic effect in photoplasma for the two-chamber cell. The present paper gives a key to the understanding of the effect of different processes (radiation, chemical, and electric) in the cell with these gas mixtures. The obtained results can be used in projecting a solar photoelectric converter based on a two-chamber device with a mixture of sodium and noble gases.