1,4-Dioxenes and 4,7-dihydrooxepines present interesting potential as motifs for the incorporation of biologically relevant molecules, agrochemicals and materials. In this study, two efficient intermolecular (3 + 2 + 1) and (5 + 2) cycloadditions for the synthesis of 1,4-dioxenes and 4,7-dihydrooxepines are achieved with gold catalysis.