Ultraviolet photodissociation dynamics of tricarbonylnitrosylcobalt, Co(CO)(3)NO, is studied by ion-imaging. The photon energy is large enough to eliminate both NO and CO ligands in this heteroleptic complex, among which state-specific scattering is observed in the NO loss channel. The velocity distributions of the NO ligands exhibit clear evidence of two pathways. NO fragments with higher and lower kinetic energies are ascribed to direct dissociation in the electronic excited state and secondary decomposition following relaxation processes, respectively. The state-specific angular distribution of the faster component corroborates the rotational alignment, indicating the bent coordination of the nitrosyl ligand in the photoexcited state. (C) 2018 Elsevier B.V. All rights reserved.