Thermal processing of Cu(In1-xCax)Se-2 thin-films grown as part of photovoltaic devices on soda-lime glass leads to the incorporation of Na impurity atoms in the Cu(In1-xGax)Se-2. Na contamination increases the photovoltaic efficiency of Cu(In1-xGax)Se-2-based devices. The purpose of this investigation is to develop a model for the chemistry of Na in Cu(In1-xGax)Se-2 in an effort to understand how it improves performance. An analysis of x-ray photoelectron spectroscopy data shows that the Na concentration is similar to 0.1 at. % in the bulk of Cu(In1-xGax)Se-2 thin films and that the Na is bound to Se. The authors propose a model invoking the replacement of column III elements by Na during the growth of Cu(In1-xGax)Se-2 thin films. Na on In and Ga sites would act as acceptor states to enhance photovoltaic device performance.