Diethylamine-modified phosphorus-containing polymer has been used as adsorbent for the preconcentration of traces amounts of Cu(II), and Zn(II). 4-(2-thiazolylazo) resorcinol was used as a chelating agent. The analytes were determined by FAAS. Various parameters such as: pH, volume of ligand, volume of elution, and eluent concentration affecting on the extraction efficiency of the polymer has been evaluated by Placket-Burman design to explore the important variables. Further were optimized by central 2(3+) star orthogonal composite design. The limits of detection for Cu(II) and Zn(II) were 2.1 and 6.3g/L, respectively. The accuracy of proposed method was checked by the analysis of TMDA 64.2 certified reference material. The method was applied to determine Cu and Zn in natural water samples.