UV irradiation of ices plays an important role in different inter- and circumstellar environments. Following the absorption of UV photons in ice, two processes compete: photodesorption and photodissociation/chemistry. From an experimental point of view it is very hard to discriminate between photodesorption and photodissociation (and resulting photochemistry). In this work we present our first attempts to distinguish both effects. The performance is demonstrated on the example of CO-ice, known not to dissociate upon UV irradiation, and CH4-ice that does fragment.