In the present work, acetylacetone phenylhydrazone (AAPH) was chemically anchored to polyurethane foam (PUF) via azo coupling of the toluidine -NH2 in PUF to active -CH2- in acetylacetone (AA) and further reaction to phenylhydrazine to give new solid phase extraction (SPE) sorbent for determination of Cu(II), Zn(II) and Mn(II) in natural and pharmaceutical samples. The AAPH-PUF was characterized by UV-VIS, IR, H-1 NMR, elemental and TGA analysis. Optimal experimental conditions were at pH 5-6, shaking time 20 min, sample flow rate 1.0 mL min(-1), and desorption by 10 mL from 0.5 mol L-1 hydrochloric acid. The limit of detection (3 sigma) was found to be 0.10, 0.12 and 0.19 mu g L-1 for Cu(II), Zn(II) and Mn(II), respectively. A preconcentration factor of 100 has been achieved for all elements. Precision (RSD%) was found to be 6.3%, 53% and 3.2% (n = 5), respectively. Successful application was achieved for environmental samples (tap water, olive leaves, and fish liver) and pharmaceutical formulation. The obtained recovery varied between 90.8% and 96.8% and RSD was under 6.7%. (c) 2012 Elsevier Ltd. All rights reserved.