There are still open questions regarding the nature of the positive effect of the presence of Na on the performance of Cu(In,Ga)Se2 based, chalcopyrite thin film solar cells, especially at low processing temperatures. Studying Cu(In,Ga)Se2 thin film devices fabricated from low-temperature coevaporated absorbers on polyimide substrates by admittance and J-V-T measurements, characteristic properties are identified for different amounts of Na present during the growth. A roll-over behavior can be directly correlated with the Na-content. X-ray photoelectron spectroscopy shows the development of a MoSe2 phase at the back contact of the device. Efficiencies of 15.1% with MgF2 antireflection coating are demonstrated.