Macrocyclic and polymeric imines 5,5' and 6,6' are obtained in excellent yields by template-free polycondensation of 1,6-bis(4-formylbenzoyloxy)hexane (1) with commercially available 4,4'-methylene-bis(cyclohexylamine) (2) and with bis(2-amino-2-methylprop-1-yl)adipate dihydrochloride (4), respectively. The degree of macrocyclization during imine synthesis strongly depends on the diamine. Matrix-assisted laser desorption-ionization time-of-flight (MALDI-TOF) mass spectrometry analysis and gel permeation chromatography (GPC) measurements show that (2) leads to more macrocyclic adducts than (4). The subsequent meta chloroperoxybenzoic acid oxidation of polyimines 5,5' and 6,6' ((M) over bar (n) = 1650-11 200 g mol(-1), (M) over bar (w) = 3800-27 350 g mol(-1)) yields the corresponding polyoxaziridines 7,7' and 8,8' consisting of macrocyclic and linear polymeric structures ((M) over bar (n) = 1750-8050 g mol(-1), (M) over bar (w) = 3250-15 800 g mol(-1)). The synthesized polyoxaziridines are relatively stable and storable at room temperature.