The deposition of surface coatings using a step-by-step approach from mutually interacting species allows the fabrication of so called “multilayered films”. These coatings are very versatile and easy to produce in environmentally friendly conditions, mostly from aqueous solution. They find more and more applications in many hot topic areas, such as in biomaterials and nanoelectronics but also in stimuli-responsive films. We aim to review the most recent developments in such stimuli-responsive coatings based on layer-by-layer (LBL) depositions in relationship to the properties of these coatings. The most investigated stimuli are based on changes in ionic strength, temperature, exposure to light, and mechanical forces. The possibility to induce a transition from linear to exponential growth in thickness and to change the charge compensation from “intrinsic” to “extrinsic” by controlling parameters such as temperature, pH, and ionic strength are the ways to confer their responsiveness to the films. Chemical post-modifications also allow to significantly modify the film properties.