The need for designing a more green approach to reversible-deactivation radical polymerization (RDRP) results in rapid evolution, enabling its facile scaling up and moving closer to industrial applications. The main factors taken into consideration are the overall process cost and its environmental impact aspects. In view of the large volumes of organic solvents applied in most polymerization techniques, producing tremendous volumes of waste and endangering the environment, the possibilities of replacing it with more environmentally friendly alternatives are highly desirable. The recent literature reports about RDRP involve employing pure, green solvents derived from natural sources, such as biomass waste or more non-conventional and certainly more cost-effective options, e.g. rain or tap water, present in everyday life extracts – coffee or lemonade, or, perhaps surprisingly, commercially available alcoholic beverages as the reaction medium. The high versatility of the proposed methods was presented by demonstrating polymerizations in a biological medium – phosphate buffer solution (PBS), imitating human fluids or cell cultures. Additional simplifications stem from the complex composition of the solvents, containing compounds, and are able to play various roles in RDRP techniques, therefore, substitution is crucial for the process ingredients such as supplementary electrolytes, reducing agents, or ligands, decreasing the number of externally added chemicals. Therefore, the main objective of this tutorial review is to teach the reader how the use of an unconventional polymerisation medium might not just be a scientific fantasy designed to validate an established concept but represent a viable and promising solution for the sustainable development of macromolecular chemistry.