The photooxygenations of the chiral allylic amine 1a, its ammonium chloride 1b, and the acylated derivatives 1c-f and 1h gave the corresponding regio- and diastereomeric allylic alpha-amino hydroperoxides 2 and 2’ through the ene reaction with singlet oxygen. For comparison purposes, also the unfunctionalized chiral alkene 2,4,5,5-tetramethyl-2-hexene (1g) was photooxygenated. While the reactions of the free amine 1a and its ammonium chloride 1b proceeded threo-diastereoselectively, for the acylated allylic amines 1c-f and (Z)-1h, as well as for the chiral alkene 1g, erythro selectivity was observed. The larger the nitrogen-containing moiety, the higher the erythro selectivity; however, for all acylated allylic amines, the stereocontrol was higher than for the alkene 1g. These findings are explained in terms of the formation of diastereomeric perepoxide-like structured exciplexes Ex or bona fide perepoxide D intermediates during the oxyfunctionalization step.