A fast and straightforward pre-concentration procedure based on solid phase extraction with a strongly acidic cation-exchanger Dowex 50 W × 8–400 was proposed to determine traces of Ca, K, Mg and Na in white sugar samples by means of flame atomic absorption spectrometry. For this purpose, 20% (m/v) white sugar solutions (100 ml) were driven through resin beds at 10 ml min−1 to retain Ca, K, Mg and Na ions and to separate sucrose that passed through unretained. Thereafter, columns were rinsed with water and elements of interest were recovered prior to measurements using 5 ml of a 2 mol l−1 HCl solution. Detection limits of 0.04, 0.05, 0.02 and 0.01 μg g−1 for Ca, K, Mg and Na, respectively, and precision of measurements within 1–3% were achieved. The proposed method enabled to determine Ca, K, Mg and Na in samples of white sugar within corresponding ranges: 0.66–0.99 μg g−1 (Ca), 2.9–12.2 μg g−1 (K), 0.53–1.57 μg g−1 (Mg) and 0.06–0.30 μg g−1 (Na). Accuracy of this sample pre-treatment procedure and analysis method was assessed by performing spikes and recovery experiments. Recoveries of added Ca, K, Mg and Na were found to be within 97–102%, demonstrating good reliability of results.