The PVC-supported ethylenediamine-copper(II) complex (PVC–EDA–Cu+2) has provided a highly efficient, active, and reusable heterogeneous catalyst for click chemistry. In this work, the PVC–EDA–Cu+2 catalyst is readily prepared by the reaction of PVC, ethylenediamine, and CuCl2·2H2O in water. The structure of the catalyst is then characterized via different analytical tools. This catalytic system shows a high activity in the multi-component synthesis of 1,4-disubstituted 1,2,3-triazoles by the click reaction of propargyl bromide, aromatic azides, and amines at room temperature. The advantages of this method are high reaction yield, short reaction time, and capability of recovering and reusing the catalyst. In addition, water, as a green medium, is used not only in the synthesis of 1,2,3-triazoles but also in the preparation of the catalyst. A number of new 1,2,3-triazole derivatives are also screened against two Gram-positive and Gram-negative bacterial strains.