The separation and identification possibilities of a number of metal-dithizonate complexes were investigated by means of a TLC-IR sequential system. Dithizonate complexes of some metal cations were prepared in a predetermined optimum pH or pH range. Optimum separation conditions of these complexes and the reproducibility of their R-f values were investigated on a series of precoated or laboratory-made TLC plates. R-f values were determined using the one-dimensional ascending technique. The precision of the procedures was determined for replicates in terms of standard deviation. Detection limits were also determined for each metal complex. The IR spectra were scanned and interpreted for precise identification after preconcentration with the wick-stick procedure for complexes giving overlapped R-f values. The complexes were able to be identified with the aid of IR absorption bands. It has been determined that these IR absorption bands will also be able to be used as reference spectral bands in possible quantitative studies. It has been concluded that an effective and successful qualitative analysis will be executable for incompletely separated complex compounds using an IR spectrophotometer as a TLC detector.