The transformation of α-acids in hops (Humulus lupulus L.) to iso-α-acids (in beer) during the brewing process is well known, but the occurrence and structure of the oxidized α-acids during hop storage are not well documented. Because an understanding of these oxidized compounds is essential to optimize the effects of oxidized hops on the quality of beer, we investigated the autoxidation products of humulone (a representative congener of α-acids) using a simplified autoxidation model. Among the oxidation products, tricyclooxyisohumulones A (1) and B (2), tricycloperoxyisohumulone A (3), deisopropyltricycloisohumulone (4), and the hemiacetal 5 of tricycloperoxyhumulone A (5′) were isolated, and their structures were elucidated for the first time. The occurrence of compounds 1–4 in stored hops was verified using LC/MS/MS analysis. We also monitored the levels of compounds 1–4 during hop storage using LC/MS/MS analysis.