A novel heterogeneous copper(I) catalyst system, which is based on readily available poly(ethyleneimine), has been used as a recyclable catalyst for Cu(I) catalyzed “click” 1,3 dipolar cycloaddition reactions of azides and alkynes in organic media. Branched poly(ethyleneimine) was first methylated and then cross‐linked with 1,9‐dibromononane. Subsequently, after the immobilization of Cu(I)Br, this system was applied for heterogeneous copper catalyzed click chemistry of a few model reagents and polymeric compounds.