Trimethylsilyl esters, AcOTMS, BzOTMS, TCAOTMS, etc., are inexpensive and chemically stable reagents that pose a negligible environmental hazard. Such compounds prove to serve as efficient dual-purpose reagents to respectively achieve acylation and trimethylsilylation of alcohols under acidic or basic conditions. Herein, a detailed study on protection of various substrates and new methodological investigations is described.