Photoexcitation of pheomelanin produces high-energy singlet oxygen and the superoxide anion, which are reactive species in damage of cellular targets. In principle, these species can be involved in processes of synthetic utility when adequate experimental conditions are defined. Here, we describe that pheomelanin performs as a selective UVA antenna for the horseradish peroxidase oxidative coupling of substituted phenols to biologically active Pummerer’s ketones under 2-methyltetrahydrofuran/buffer biphasic conditions. In this system, singlet oxygen is scavenged by conversion of 2-methyltetrahydrofuran into the corresponding organic hydroperoxide, while the superoxide anion is dismutated into hydrogen peroxide. Both these intermediates are able to oxidize the active site of horseradish peroxidase triggering the oxidative coupling reaction. Trimer derivatives, produced by addition of phenoxy radicals on preformed Pummerer’s ketones were also isolated, suggesting the possibility to further improve the structural complexity of the reaction products.