The NH3···CO complex can be considered an important building block for cold synthetic astrochemistry leading to the formation of complex organic molecules, including key prebiotic species. In this work, we have studied the radiation-induced transformations of this complex in Ar, Kr, and Xe matrices using FTIR spectroscopy. On the basis of comparison with the quantum chemical calculations at the CCSD(T)/L2a_3 level of theory, it was found that the initial complex had the configuration with hydrogen bonding through the carbon atom of CO. Irradiation of the matrix isolated complex with X-rays at 6 K leads to the formation of a number of synthetic products, namely, HNCO (in all matrices), formamide NH2CHO, NH2CO, and HNCO-H2 (in argon and krypton). The matrix effect on the product distribution was explained by the involvement of different excited states of the complex in their formation. It was suggested that formamide results from the singlet excited states while other species mainly originate from triplet excited states. The latter states are efficiently populated through ion-electron recombination (in all matrices) and through intersystem crossing (particularly, in xenon). High yield of the recombination triplet states is a feature of the processes induced by high-energy radiation (in contrast to direct photolysis). NCO, CN, and NO were found as minor secondary products at high adsorbed doses. The astrochemical implications of the obtained results are discussed.