A new p-tert-[(dimethylamino)methyl]-1,3-bisglyciyl-calix[4]arene functionalized aminopropylpolysiloxane resin (APPS-CA) has been prepared and investigated for selective solid-phase extraction (SPE) of trace Cr (III), Cu (II), Ni (II), Co (II) and Zn (II) prior to their determination by inductively coupled plasma optical emission spectrometry (ICP-OES). The characterization of the surface modification was performed on the basis of FT-IR spectroscopy, elemental analysis and thermal gravimetric analysis. The separation/preconcentration conditions of analytes were investigated, including effect of pH, the shaking time, the sample flow rate and volume, the elution condition, the interfering ions and stability test. At pH 4.0, the maximum adsorption capacity of Cr (III), Cu (II), Ni (II), Co (II) and Zn (II) were 47.2, 34.3, 52.8, 29.8 and 36.4 mg g(-1), respectively. The adsorbed metal ions were quantitatively eluted by 2.0 mL of 0.5 mol L(-1) HCl. Common coexisting ions did not interfere with the separation. According to the definition of International Union of Pure and Applied Chemistry, the detection limits (3 sigma) of this method were found to be 0.58, 0.33, 0.47, 0.61 and 0.14 ng mL(-1) for Cr (III), Cu (II), Ni (II), Co (II) and Zn (II), respectively. The relative standard deviation under optimum conditions is less than 4.0%. The application of this new adsorbent to preconcentration trace Cr (III), Cu (II), Ni (II), Co (II) and Zn (II) of two water samples gave high accurate and precise results.