Silica gel has been used as a stationary phase in combination with surfactant-mediated acidic eluents for thin-layer chromatography (TLC) of 14 metal cations. Several combinations of mobile-phase systems comprising different surfactants (anionic, cationic, and nonionic) and carboxylic or mineral acids have been tested for rapid and reliable separation of metal cations. The results obtained on plain silica gel were compared with those obtained on plain alumina, cellulose, and keiselguhr, as well as on mixed adsorbents. The TLC system constituting silica gel as a stationary phase and 0.001 M aqueous sodium bis(2-ethyl hexyl) sulfosuccinate plus 10 M aqueous formic acid (1:1, v/v) as a mobile phase was identified as the most favorable system for the separation of coexisting Al3+, Fe3+, and Ti4+ in the presence of common organic and inorganic impurities. The proposed method is rapid and is suitable for identification and separation of Al3+, Fe3+, and Ti4+ from sea, river, tap water, and bauxite ores. The separation of microgram quantities of Al3+ from milligram quantities of Fe3+ or vice versa and parameters such as limits of detection, reproducibility, and repeatability were studied. Quantitative determination of Al3+ in bauxite ores was done by TLC spectrophotometer.