The UV-induced and catalyst-free photoiniferter surface grafting using xanthate RAFT agents is studied. First, a novel silane containing a xanthate RAFT agent moiety is synthesized and successfully grafted onto a silicon wafer as confirmed by secondary ion mass spectrometry (SIMS). Next, using only methyl acrylate, solvent and UV light (365 nm) polymer brushes are grafted rapidly from the surface with film thicknesses up to 25 nm reached within half an hour. The obtained polymer films are thoroughly analyzed by X-ray photoelectron spectroscopy (XPS), ToF-SIMS, and AFM. (c) 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2002-2007