A separation and preconcentration procedure based on solid-phase extraction of Cu(II) and Pb(II) as their Sudan III chelates on polyhydroxybutyrate-b-polydimethyl siloxane (PHB-b-PDMS) block copolymer disc has been established. Various analytical parameters including pH, amount of Sudan III, eluent type and volume, sample volume, flow rates were optimised. The effects of concomitant ions on the retentions of the analyte ions on PHB-b-PDMS disc were also examined. The detection limits for Cu(II) and Pb(II) were found to be 2.3 and 4.9 μgL−1, respectively. Preconcentration factor was found to be sixty. Relative standard deviation was found to be 5%. The accuracy of the method was confirmed by analysing certified reference materials (TMDA 54.4 fortified lake water and NIST 1515 Apple leaves). Optimised method was applied to determine the analyte ions in various water and food samples from Turkey.