Abstract: A review of new results on the application of layer-by-layer (LbL) chemical assembly procedures to the production of thin-layer structures on the surfaces of various substrates in order to develop active elements (AEs) of chemoresistive gas sensors for the determination of inorganic and organic compounds in air and controlled gas atmospheres is presented. The LbL assembly procedures and their features, such as the possibility of synthesis under the conditions of soft chemistry, the precise setting of the thicknesses of applied layers, and the production of multilayers consisting of individual layers with predicted compositions, are considered. Charge transfer between analyte molecules in the layers and oxidation–reduction centers on the AE surface is briefly discussed, and conditions for the functioning of optimal AEs are formulated. The capabilities of the LbL assembly method to precisely control the thickness of each layer in a multilayer system on the electrode surface and thus directionally change the sensor response and select a layer responsible for the best practically important characteristics are emphasized. The role of catalysts in these processes is noted. The results of original publications on the application of LbL assembly procedures to the development of a wide range of AEs for sensors are presented, and the analytical characteristics of the sensors are compared. In conclusion, the prospects for using these procedures in the manufacture of new AEs with high sensitivity and selectivity and a short response time are considered.