Surface silylation of silica has been carried out by a sequential synthetic route. The hydroxylated surface has been functionalized with 3-chloropropyltrimethoxysilane or 3-aminopropyltrimethoxysilane. "End-capping" of residual silanol surface sites has been effected by reacting with chlorotrimethylsilane, followed by attachment of a secondary amine. Additional results on three macrocycle compounds are reported. The synthetic route has been tracked by laser Raman microprobe/spectroscopy, which has been shown to be a convenient, flexible and discriminating probe of the surface chemistry of organosilane monolayers.