The photochemistry of CO(CN)(2) in cryogenic matrixes has been investigated employing pulsed laser excitation at 193 nm. During irradiation, the parent molecule, the intermediate, and the final photoproducts were monitored by IR spectroscopy. Four new species were identified including the isocyano isomer of the parent NCC(O)NC, cyanogen NCCN, isocyanogen CNCN, and CO according to spectroscopic features and ab initio calculations. After prolonged irradiation, the only remaining species were CO and the two isomers NCCN and CNCN. A reaction scheme is proposed which is in agreement with the first dissociation step being a branching of the decay path into the radical channel to CN + OCCN and the molecular channel to CO + (CN)(2). The caged radicals of the former reaction either recombine to the parent molecule and its isomer which are both photolyzed again or they react directly to the stable and final products.