Compared to universal radical difunctionalization of alkenes that are performed with organic solvents, such reactions with water as the sole solvent are rarely reported. Concerning the global consensus on environmental issues, we developed herein a method for radical oxyazidation of alkenes in pure water. This reaction allows the constructions of C-N and C-O bonds in a one pot process. Styrenes, 1,3-dienes, and unactivated alkenes can react smoothly under mild and environmentally benign conditions to afford a wide scope of functionalized azides in excellent yields and selectivity.