An instantaneous single step immobilization of dithizone (DZ) on silica gel (SG) in an environmentally benign solvent was made by using dimethyldichlorosilane as a silane-coupling-reagent. The material, {SiO₂}@DZ (Mol.Wt. 5816g.mol⁻¹; particle-sizes: 200±20μm; SA_BET: 280.3m².g⁻¹) was found to be inert (thermally up to 353K and against all mineral acids) and utilized for selective sample clean up of Cd(II). XPS supported di-nuclear-{Cd₂(OH)(H₂O)}³⁺ was quantitatively sorbed at sorbent-HOMO (quantified as 172 μmol.g⁻¹) as a weak enfold, {sorbent-HOMO}(:){Cd₂(OH)(H₂O)³⁺} (stabilized by 0.14 kJ.mol⁻¹) at pH 4.5 and subsequently retrieved (>98%) with 3 mL 0.01 mol.L⁻¹ HClO₄. ‘Sorption-desorption-equilibration-pathway’ may be expressed as ‘reversible process’ regulating by {H₃O}⁺ emphatically. High level of breakthrough capacity (329 μmol.g⁻¹), enrichment-factor (302) and reusability (>800cycles) depicts the highness of the synthesized sorbent.