A silver(I)-mediated oxidative N–H/C(sp³)–H coupling of NH-azoles with ethers has been developed. Various substrates were well N-alkylated in this methodology and the corresponding desired products were given in moderate to good yields. Moreover, the late-stage alkylation of bioactive molecules was achieved. This protocol involved C(sp³)–N bond formation via a radical pathway generated in the presence of low cost and readily available heptafluoroisopropyl iodide (i-C₃F₇I). Generally, this reaction features excellent functional group compatibility, broad substrate scope, good regioselectivity, and fast access to pharmaceuticals such as SQ 22536.