Nowadays, polyelectrolytes play an essential role in the development of new materials. Their use allows creating new properties of materials and surfaces and vary them in a wide range. Basically, modern methods are divided into three areas—the process of layer‐by‐layer deposition, free‐standing films, and hydrogels based on polyelectrolytes. Layer‐by‐layer assembly of polyelectrolytes on various surfaces is a powerful technique. It allows giving surfaces new properties, for example, protect them from corrosion. Free‐standing films are essential tools for the design of membranes and sensors. Hydrogels based on polyelectrolytes have recently shown their applicability in electrical and materials science. The creation of new materials and components with controlled properties can be achieved using polyelectrolytes. This review focuses on new technologies that have been developed with polyelectrolytes over the last five years.