In this study, a novel functional nanocomposite was synthesized, characterized and selectively used in pH-controlled separation, pre-concentration and speciation analysis of Cu(I) and Cu(II) from sample matrices where extraction is assisted, facilitated and greatly enhanced by ultrasound energy. The hydrophilic composite material functionalized with tris(2-hydroxymethyl)aminomethane (Tris) and Fe3O4 NPs was characterized in detail by ATR-FT-IR, H-1 NMR, XRD, EDX peaks and SEM images. After optimization of the main variables influencing extraction efficiency such as pH, volumes of buffer, modified copolymer in acetone, CTAB and Triton X-114 at fixed concentrations including sonication conditions, the Cu(I) and Cu(II) were monitored against a blank at 347 nm by micro-volume UV-vis spectrophotometer. A good linearity was obtained in the range of 2-140 and 5-150 mu g L-1 for Cu(II) and Cu(I) with r(2) >= 0.993. The limits of detection (LODs) of 0.66 and 1.60 mu g L-1 for each analyte, were obtained from a pre-concentration of 70-fold. After validation, the method was applied to speciation of Cu(I), Cu(II), and total Cu in the pre-treated and diluted beverage samples before and after pre-oxidation of Cu(I) to Cu(II) due to be more sensitive of extraction process to Cu(II) at pH 6.0. The results were also compared with those obtained by FAAS analysis to ensure the reliability of the results. It was observed that there was a statistically good agreement between the results of both methods.