Hyperbranched epoxide‐amine adducts were synthesized by a one‐pot microwave (MW) assisted reaction. 4‐(2,3‐epoxypropyl‐1‐oxy)benzonitrile was hydrogenated using Pd/C under microwave conditions, forming the AB2 monomer 1‐aminomethyl‐4‐(2,3‐epoxypropyl‐1‐oxy)benzene. Depending on the reaction temperature this monomer immediately reacts to give hyperbranched epoxide‐amine adducts. Mass spectrometric investigations proved the formation of a homologous series of oligomers containing up to six repeating units. Due to the complexing properties of the poly(amino alcohol) moieties in the presence of Cu2+ ions, large aggregates were formed.