A column solid-phase extraction method for the separation and preconcentration of copper, zinc, and iron at trace levels has been established prior to their flame atomic absorption spectrometric determinations. Analytes from 0.5 M KSCN in a 1 M HCl solution were recovered using of an Amberlite XAD-7 column. The chemical variables affecting the analytical performance of the combined methodology including reagent amounts, sample volume, flow rates of sample, and eluent solutions on the quantitative recoveries of analyte ions were studied and optimized. The presented method was applied to the analysis of natural waters and red wine sample with satisfactory results (recoveries greater than 95%, relative standard deviations (RSD) lower than 8%). The accuracy and precision of the method were confirmed by the analysis of three kinds of certified reference materials (NRCC-SLRS-4 riverine, water, SRM 1515 apple leaves, and SRM 2711 Montana soil).