Abstract: Through a conception of molecular design, only via two steps of macromolecule reactions, it was realized to synchronously synthesize and immobilize N-hydroxyphthalimide (NHPI) on crosslinked polystyrene (CPS) microspheres, and the heterogeneous catalyst microspheres CPS-NHPI were obtained. Via Friedel-Crafts acylation reaction, phthalic anhydride (PA) was bonded on the surfaces of CPS microspheres using trimellitic anhydride chloride (TMAC) as reagent and Lewis acid as catalysts, resulting in the modified microspheres CPS-PA. Subsequently, the microspheres CPS-PA were allowed to be reacted with hydroxylamine hydrochloride, namely imidation reaction was carried out, preparing the microspheres CPS-NHPI, on which the catalyst group NHPI was immobilized. The effects of the main factors on the acylation reaction were examined. On the basis of characterizing microspheres CPS-NHPI by Fourier Transform Infrared spectroscopy (FT-IR), Scanning Electron Microscope (SEM) and chemical analytical method, the microspheres CPS-NHPI were used in the oxidations of ethylbenzene and cyclohexane with molecular oxygen, respectively, and the catalytic activity of CPS-NHPI were examined preliminarily. Results show that the solvent property and the kind of Lewis acid catalysts effect the acylation reaction greatly. The suitable solvent is the mixed solvent of CHCl₃ and dimethylacetamide (DMAC) with a volume ratio of 7:3, and the appropriate Lewis acid catalyst is SnCl₄. The results of primarily exploring reveal that a compositional catalyst system constituted by microspheres CPS-NHPI and a little of Co(OAc)₂ displays fine catalytic activity in the oxidation reactions of ethylbenzene and cyclohexane with molecular oxygen as oxidant.The conversion rate of ethylbenzene oxidation to acetophenone is 37% for 35 h, and the conversion rate of cyclohexane oxidation to cyclohexanone is 21% for 30 h.