3-[(3-(Trisilyloxy)propyl)chloride]-1-methylimidazolium tribromide ionic liquid supported on MCM-41 [nano-MCM-41@(CH2)3-1-methylimidazole]Br3 as a novel heterogeneous nano-catalyst was easily prepared and characterized using FT-IR spectroscopy, scanning electron microscopy, X-ray diffraction, thermogravimetric analysis, differential thermal analysis, and differential thermogravimetric analysis. This catalyst was successfully applied for selective trimethylsilylation of various alcohols (primary, secondary, and tertiary alcohols) and also various phenols using hexamethyldisilazane in dichloromethane at room temperature to their corresponding trimethylsilyl (TMS) ethers. This method has a lot of advantages such as short reaction time, good to excellent yield of products, and ease of recovering and reusing the catalyst.