New sulphoxide modified resins were synthesized using poly(styrene-co-divinylbenzene) (PS-DVB) as matrix. Infrared spectroscopy and elemental analysis were used for characterisation. Solid-phase extraction of Pt IV , Ru III and Ru IV from acidic chloride solutions was performed via batch experiments. Influence of spacer length between sulphoxide and matrix (ethylene, hexamethylene), substitution of sulphoxide (R 1 : ethyl, hexyl, phenyl) and bead size of PS-DVB (spherical beads: d 50 <155μm, d 50 <80μm; powder: d 50 <30μm) on adsorption was investigated subjected to acidity. Experimental results showed that ethyl substituted sulphoxide immobilised onto ground PS-DVB and hexamethylene spacer exhibited best adsorption properties. Different kinetic models and isotherms were fitted to the experimental data to identify extraction mechanism. Pt IV was quantitative sorbed at [HCl]⩽0.1mol/L whereas Ru III and Ru IV sorption ranged between 90% and 95% at [HCl]⩾5mol/L. Desorption was reached using a solution of 0.5M thiourea (Tu) in 0.1M HCl at 90°C. Separation of Pt IV and Ru III occurred at [HCl]⩽0.1mol/L whereas Pt IV was extracted and Ru III remained in solution. A further separation was achieved by extracting Pt IV and Ru IV at 5M HCl followed by sequential elution of Pt IV with concentrated HCl and Ru IV with 0.5M Tu in 0.1M HCl at 90°C.