A novel method for the regioselective meta substitution of calix[4]arenes based on the direct C–H azidation of an amino-substituted calixarene immobilized in the cone conformation is described. Reaction with trimethylsilyl azide and tert-butyl hydroperoxide in the presence of CuBr as a catalyst, provided, depending on the stoichiometry, mono- or bis-azide-substituted derivatives in good yields under mild reaction conditions. meta-Azido calixarenes represent potentially valuable synthetic intermediates for the preparation of calixarenes possessing unusual substitution patterns as demonstrated by a click reaction with p-nitrophenyl acetylene.