Biosurfactants account for about 12% of the global value of the surfactant market, which is currently dominated by synthetic surfactants obtained from fossil sources. Yet, the production of biosurfactants from renewable feedstock is bound to increase, driven by the increasing pressure from both society and governments for chemistry-based industries to become more ecofriendly and economically sustainable. A photo-chemical oxidation process is reported here, yielding new biosurfactants from urban biowaste in water that perform as a solvent and terminal oxidant reagent at room temperature without the addition of conventional oxidants and catalysts. Products with 200–500 kDa molecular weight are obtained. They lower the surface tension of water down to 34 mN/m at 0.5–2 g/L concentration. The estimated cost is rather low (0.1–1.5 EUR/kg), which is competitive with the cost of synthetic surfactants but much lower than the cost of the best-performing bacterial surfactants. For the implementation of the photo-chemical oxidation process at the industrial level, the results suggest that the new biosurfactants obtained in the present work may not reach the performance level of the best-performing bacterial surfactants capable of lowering the surface tension of water down to 28 mN/m. Yet, the biosurfactants produced by the photo-chemical process have a greater chance of being marketed on large scales.