A simple protocol for the selective azidation of alcohols is developed using a solid acid hybrid of a povidone and phosphotungstic acid (PVP–PWA) using azidotrimethylsilane as an azide source at room temperature. In a broad substrate scope, various activated as well as unactivated benzylic and diphenyl alcohols were treated smoothly with TMS-N₃ to selectively produce only azide products with excellent yields in a very short reaction time of 2 h. FT-IR confirmed the stability of the catalyst with retention of the Keggins structure after the reaction. Recycling experiments demonstrated the reusability of the PVP–PWA (3 : 1) several times without losing its original activity.