Nonionic surfactants containing a polyoxyethylene headgroup are known to slowly undergo oxidative degradation when exposed to air. The oxidation, which starts by abstraction of a hydrogen atom from a methylene group in a-position to an ether oxygen, is accelerated by metal ions. Silver ion mediated oxidation of a technical grade surfactant of this type, Brij 30, was investigated in two types of self-assembled systems, a water-in-oil microemulsion and a liquid crystalline phase. It was found that in both systems the longer homologues, i.e., the surfactant homologues that carry a longer polyoxyethylene chain, decompose faster than the shorter homologues. This trend was found to be more pronounced when the surfactant is present in a liquid crystal than in a microemulsion. The difference is explained in terms of differences in accessibility of the polyoxyethylene chains to the silver ions.