摘要： Fluoroalkyl end-capped vinyltrimethoxysilane oligomer [RF-(CH2CHSi(OMe)3)n-RF; n = 2, 3; RF = CF(CF3)OC3F7] undergoes sol–gel reactions in the presence of hexagonal boron nitride (h-BN) nanoparticles under alkaline or acidic conditions at room temperature to afford the corresponding fluorinated oligomeric silica/h-BN nanocomposites in good isolated yields (≥ 80%), respectively. The fluorinated oligomeric silica/h-BN nanocomposites thus obtained were found to exhibit a good dispersibility toward the traditional organic media including water. These two kinds of fluorinated nanocomposites were applied to the surface modification of poly(methyl methacrylate) (PMMA). The fluorinated nanocomposites prepared under alkaline conditions can give not only a good oleophobic characteristic imparted by longer fluoroalkyl groups in the composites but also the higher fluorescent emission related to the presence of h-BN on the only surface side of the modified PMMA film. In contrast, the fluorinated nanocomposites prepared under acidic conditions can provide a good oleophobic characteristic and a higher fluorescent emission on both the surface and even on the reverse side of the PMMA film. Such unique controlled surface modification ability will be discussed by 29Si solid-state NMR spectra of these two types of the nanocomposites.