Immobilization of 4-vinyl pyridine (4-VP) onto silica gel (SG) and its coordination with cupric ion (SG-4-VP -> Cu2+) leading to a new solid phase extractor has been carried out by a simple chemical technique. Immobilization and coordination reactions are characterized by chemical, FTIR, UV, and thermo-gravimetric analysis. The role of cupric ion on Cr(VI) binding capacity of the synthesized organic-inorganic hybrid material has been elucidated. The silica gel immobilized 4-VP/Cu2+ complex (hybrid material) is tested for selective extraction and pre-concentration of Cr(VI) from aqueous solution. The Cr(VI) binding behavior of the synthesized material is studied at different pH, time, and temperature of the medium in both competitive and non-competitive conditions.