Two types of solid supports synthesized for the preparation of heterogeneous catalysts. 2-Pyridinecarboxaldehyde ligand was anchored on commercially available revere phase 3-aminopropyl-functionalized silica gel followed by Cu metal immobilization. Amino-functionalized reverse phase silica with alkyl end capped amino groups was used to induce hydrophobic behavior in the polar silica support. Poly(NIPAM-co-4-VP) was synthesized from N-isopropylacrylamide and 4-vinylpyridine with a 1:1 monomer ratio and followed by Cu metal immobilization. Poly(NIPAM-co-4-VP) undergoes a phase transition at the low critical solution temperature with a change from the hydrophilic to the hydrophobic core in a hydrophilic solvent. These properties of the catalysts enabled the [3+2] cycloaddition in water and showed good results. These catalysts are stable in air and reusable over several times with negligible leaching of Cu metal. Various characterization methods including XPS, ICP, DSC, SEM, BET, 1H- and 13C- NMR, solid NMR are used to verify the efficiency of the catalysts.