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Multi-walled carbon nanotubes (MWCNTs) supported HSiW/MWCNTs was successfully prepared and characterized by Fourier transform infrared spectoscopy, X-ray powder diffraction, transmission electron microscopy and N2 adsorption–desorption test. Its catalytic performance for the catalytic Baeyer–Villiger oxidation of cyclic ketones with 30 % H2O2 as oxidants was investigated. It was found that HSiW/MWCNTs was very efficient to transform of some cycloketones to the corresponding lactones with high conversions as well as selectivities. Factors affecting the oxidations and the reusability of the catalyst were also investigated. It was found that the catalyst can be reused seven times in the catalytic oxidation reaction of cyclopentanone without obviously catalytic activity losing in the oxidation. A supported solid acid of HSiW/MWCNTs was used as efficient catalyst for the Baeyer–Villiger oxidation of ketones. High cyclopentanone conversion (98 %) and e- valerolactone selectivity (99 %) were obtained. The catalyst can be reused at least seven runs in the oxidation of cyclopentanone.