A complete dissociation progression of aniline under VUV irradiation over the entire relevant internal energy range and inclusive of all decay channels is presented. The onset energy and breakdown curve was found to be instrumental in selecting relevant pathways out of multiple possibilities predicted by computation for all significant decay channels. The relevance of the ring contraction in the formation of the intermediate five-member ring structure and its consequences for the important channels such as HNC, H and HNCH losses are highlighted. In addition, a potential route for the formation of previously unexplored and astronomically important fragments HNCH and HCCN has been found. It could be deduced that aniline differs from its bicyclic nitrogenated counterpart, naphthalamine, as ring contraction in aniline is found to be favourable over ring expansion. Moreover, the role of H migration-assisted isomerization is highlighted in the context of the formation of astronomically important species.
