Salicylaldoxime-immobilized silica gel was used as an effective sorbent for solid-phase extraction of Cu(II), Ni(II), Co(II), and Zn(II) ions from aqueous solutions. Conditions for effective adsorption are optimized with respect to different experimental parameters in both batch and column processes. The feasibility of the process was judged from both kinetic and thermodynamic points of view. The lower limit of detection as well as the enrichment factor for each metal ion was evaluated. The repeatability of the process and the regeneration of the solid phase were also evaluated. Analytical utility is illustrated in real aqueous samples generated from an industrial effluent, a pharmaceutical preparation, and a biological sample.