Barrier materials have wide applicability in both professional (military, medical, industrial) and non-professional (leisure and sports) fields. This paper focuses on the preparation of real conductive polymer (CP) sensors, for the study of the permeation of volatile toxic compounds through barrier materials. Use of such a CP sensor can help improve the quality of barrier materials used in protective clothing. Several types of platforms have been manufactured or purchased for use as comb sensors with different electrode dimensions, and a suitable method of applying the detection layer of conductive polymers (polyaniline and poly-pyrrole) has been developed. Prepared sensors were obtained using various technologies and were assessed not only for response to exposure to vapors of volatile toxic substances, but also for the possibility of their incorporation into a permeation cell, in order to expand the possibilities of using existing permeation devices. The resulting conductivity of the surface film ranges from 50 to 10,000 μS/cm. When exposed to ethanol vapors, the conductivity of the sensors dropped significantly and returned to the original value after exposure ended. The conductivity of the B12 CP sensor was in the range of 10–100 mS/cm and is considered the most valuable tested sensor. CPs deposited on this substrate have very high sensitivity in units of ppm (in special cases, even ppb) within the detection of analytes (in this case toxic vapors of ethanol, acetic acid) and the ability to return to initial (zero) conductivity.