The photodissociation of CO(CN) 2 at 193 nm has been studied by probing the nascent CN fragments. Two energetically different CN species were identified, a rotationally and vibrationally hot one characterized by T r∼2300 K and T v∼3600 K, and a cold one exclusively in v=0 with T r∼410 K. The hot CN together with OCCN stems from the α-cleavage while the cold CN, which accounts for about 18% of all CN fragments, is from the spontaneous secondary decay OCCN→CN+CO thus confirming the three-body decay to be a sequential process.