Nowadays in chronic diseases structure mental derangement leading to disability and mortality of population comes to the front. As a result of illicit traffic of drugs extension, using psychoactive medicinal agents by drug abusers for intensification of intoxication and alleviation of abstinence syndrome has been fixed to increase. It results in occurrence of poisonings. The main goal of the work is a development of strategy of chemical-toxicological analysis of psychoactive medical agents useable for combined poisonings via thin-layer chromatography method. The research offers the results of studying the chromatographic behaviour of tofisopam and fluoxetine combined with psychoactive medicinal agents on chromatographic plates "Sorbfil UV-254" and "Armcorb UV-254" in general solvent systems. It is shown that separation of psychoactive substances does not occur accurate enough. Therefore, it is necessary to develop particular chromatographic systems. A system of composition of toluol - acetone - 25% solution of ammonia is revealed and can be recommended in screening while carrying out a nondirectional analysis of tofisopam and fluoxetine. In this system, all combinations under research are detected. A search of particular chromatographic systems was carried out by changing the quantity of toluol, acetone and ammonia. It is established that solvent systems of toluol - acetone - 25% solution of ammonia in a ratio 50:50:1 and 50:50:4 are optimal for identification of combinations with tofisopam and fluoxetine accordingly. The developed method allows detecting tofisopam and fluoxetine in urine on a preliminary step of research both individually and in combinations with psychoactive medicinal agents.