In previous work, we used 2-phenylbenzoxazinone-based compounds to functionalize polymers with oxazinone groups. By reaction of these oxazinone-functionalized polymers with amino group containing polymers, block and graft copolymers were obtained. As a proof of concept, we also synthesized A2-B4 hybrid networks by conversion of an oxazinone-terminated 4-arm poly-Ɛ- caprolactone star with a linear amino-terminated polypropylene glycol prepolymer. A major advantage of the oxazinone-amine reaction is their controllable reactivity. By introducing electron withdrawing substituents on the oxazinone group and varying the reaction temperature, the course of the reaction can be significantly influenced, offering great potential for the synthesis of welldefined ACNs.