Carboazidation and diazidation were carried out on 1,3-diene compounds using TMSN3 as the azide source and MeCN as the cyanoalkylation reagent. This method exhibits excellent functional group tolerance, a broad substrate range, and a short reaction time, providing an effective pathway for synthesizing valuable azides. Our report introduces an unprecedented strategy for the carboazidation and diazidation of 1,3-dienes, with mechanism studies indicating that the reaction involves a radical pathway.