• New aryltriazenes are synthesized and fully characterized in solution by means of different analytical techniques. • The photoreactivity depends on the kind and position of the chemical substituents of the phenyl ring and on the solvent used. • The photoproducts are evaluated using GC-MS and they depends on the solvent used. • The light induced reaction of the nitro derivative is performed in polymer matrices. • The reactivity changes with the polymer used. Triazenes are molecular systems that undergo a photolysis with the evolution of molecular nitrogen. A set of aryltriazene bearing different substituents are synthesized and characterized. The photoreaction is studied in solution by means of UV-vis spectroscopy showing a large dependence of required doses and UV-vis spectrum evolution on the substituent position and character. The structural changes upon the photolysis are also probed using vibrational spectroscopy (IR and Raman). Moreover, GC-MS spectroscopy is employed to retrieve the structure of the main photoproducts. The most promising derivative, in terms of stability and band position is incorporated in different polymer matrices, both thermosetting and thermoplastic; its photoreaction is studied in correlation with the polymer structure.