We report the first general synthesis for O-alkylarylhydroximoyl azides. This synthesis produces a single geometric isomer. These organoazides offer potential routes to heterocylcic systems containing the oxime ether substituent of specific stereochemistry. A series of these compounds with ring substituents varying from electron-donating to electron-withdrawing have been produced. The stability of these compounds and their reactivity in Schmidt-type rearrangements and in cycloaddition reactions will be discussed.