We demonstrate that niobium oxide exchanges oxygen with the atmosphere when illuminated by simulated sunlight. The oxygen exchange was found to take place for pristine niobium oxide films when illuminated in an oxygen atmosphere and when illuminated in an operational hybrid solar cell. The oxygen exchange was demonstrated using O-18(2)-isotopic labeling in combination with time-of-flight secondary ion mass spectrometry (TOF-SIMS) imaging analysis of devices and oxide substrates. TOF-SIMS depth profiling confirmed O-18 incorporation throughout the device in hybrid solar cells. The results are discussed in the context of hybrid solar cell stability and illuminate one of the degradation paths.