The present book deals with the layer-by-layer assembly of different polyelectrolyte pairs, PDACMAC/PSS, PAH/PAA, PLL/PGA and CHIT/DEX onto a negatively charged P(NiPAM-co-MAA) microgel. The following chapters will describe in detail the influence of the polyelectrolyte nature and molecular weight as well as the pH and ionic strength of the dipping solutions on the behaviour of the coated ensembles. The temperature responsiveness, electrophoretic mobility, temporal stability, morphology and bilayer thickness of different systems will be described. Further, the mechanisms of interaction between the microgel and the polyelectrolytes will be analyzed. This study demonstrates that the properties of multilayers confined onto microgels can be finely tuned by adjusting the assembly conditions. The approach illustrated herein is a simple, versatile and interesting method to integrate polyelectrolytes with microgels for the design of new materials that have potential use in biomedical applications like controlled loading and release of substances.