The ammoximation of cyclohexanone using preformed hydrogen peroxide (H2O2) is currently applied commercially to produce cyclohexanone oxime, an important feedstock in nylon-6 production. We demonstrate that by using supported gold-palladium (AuPd) alloyed nanoparticles in conjunction with a titanium silicate-1 (TS-1) catalyst, H2O2 can be generated in situ as needed, producing cyclohexanone oxime with >95% selectivity, comparable to the current industrial route. The ammoximation of several additional simple ketones is also demonstrated. Our approach eliminates the need to transport and store highly concentrated, stabilized H2O2, potentially achieving substantial environmental and economic savings. This approach could form the basis of an alternative route to numerous chemical transformations that are currently dependent on a combination of preformed H2O2 and TS-1, while allowing for considerable process intensification.