A novel and efficient protocol for the synthesis of organic ammonium tribromides (OATBs) is developed by using inexpensive and eco-friendly periodic acid as an oxidant for the conversion of Br- to Br-3(-). The method does not use any mineral acid and metal oxidants. The protocol is utilized to synthesize a new bis(tribromide) viz., 1,1'-(ethane-1,2-diyl)dipiperidinium bis(tribromide) (EDPBT). EDPBT is investigated as a catalyst in the silylation of alcohols and thiols by HMDS (hexamethyldisilazane) under solvent-free conditions.