Trimethylsilylation of alcohols was achieved using 1,1,1,3,3,3-hexamethyldisilazane(HMDS) as silylating agent,in the presence of polyvinylpolypyrrolidonium tribromide in acetonitrile at room temperature.Also a variety of alcohols were converted into alkyl formates by ethyl formate and a catalytic amount of polyvinylpolypyrrolidonium tribromide under solvent free conditions at room temperature. Trimethylsilylation of alcohols was achieved using 1,1,1,3,3,3-hexamethyldisilazane (HMDS) as silylating agent, in the presence of polyvinyl pyrrolidonium tribromide in acetonitrile at room temperature. Al a a variety of alcohols were converted into alkyl formates by ethyl formate and a catalytic amount of polyvinylpolypyrrolidonium tribromide under solvent free conditions at room temperature.