A comparison of the chromatographic behavior of benzoic acids on normal (silica gel), reversed (RP-18), and polyamide-11 plates using thin-layer chromatography (TLC) with controlled gas phase inside the chamber has been performed. This variant of TLC is based on the use of a gas phase moving over the TLC plate for regulation of the stationary and mobile phases as well as the acid—base properties of analytes during the separation process. The feasibility of such an approach is illustrated by the separation of benzoic acid derivatives using carbon dioxide, ammonia, and acetic acid vapor. It was shown that a gradual change of mobile phase acidity makes it possible to enhance separation efficiency and selectivity, this effect being dependent on the type of the stationary phase. The most considerable change in the retention of benzoic acid derivatives was observed for normal-phase plates with silica gel or silica sol, or starch binders used as the stationary phase. An alteration of surface acidity for polyamide and RP-18 plates is not so pronounced as for silica gel ones so that a smaller change in chromatographic parameters of benzoic acid derivatives was observed.