Lifetime guarantees of more than 20 years are a target for the long-term stability of solar modules. An important point for the future of CIGS solar cells is to understand the impact of metastable behaviour on long-term stability. Accelerated ageing under open-circuit conditions leads to a drop in open-circuit voltage (Voc). A decrease in the net doping density is responsible for the drop in Voc and consequently the drop in the photoluminescence (PL). In the initial state the electroluminescence (EL) ideality factor exhibits a value close to unity, as expected from theory. After the dark anneal an increase in the EL ideality factor is observed, and an EL measurement at constant voltage shows a decrease in EL: both these behaviours are due to a pile-up of negative charges at the heterointerface. The application of a positive bias or an illumination during the endurance test leads to an optimization of stability. This paper shows that PL and EL can distinguish between bulk and interface properties and are well suited for the detection of degradation mechanisms.