AbstractWine‐based miniemulsion was used as polymerization medium for the synthesis of non water‐miscible polymethacrylates for the first time. The solution, inspired by green chemistry principles, is an interesting alternative to the use organic solvent application in polymer synthesis. The paper presents an unusual but cost‐effective solution, which, due to the presence of reducing agents present in wine, allowed the synthesis of polymethacrylates according to the low ppm atom transfer radical polymerization (ATRP) concept, but without the injection of additional reducing agents. Among the tested liquors were: (a) a white semi‐sweet wine (Tokaj—TK); (b) ruby sweet wine (Carlo Rossi—CR); (c) raspberry homemade wine (Wino Jana—WJ), and (d) dark red dry wine (Merlot—ME). Interestingly, the use of dry wine with ~300 ppm by wt of CuII/tris(2‐pyridylmethyl) amine (TPMA) as hydrophilic catalyst resulted in the controlled synthesis of poly(n‐butyl acrylate) (PnBA), poly(n‐butyl methacrylate) (PnBMA), and poly(tert‐butyl acrylate) (PtBA) characterized by a narrow molecular weight distribution (Đ = 1.18–1.50). The final structures of the synthesized polymers were comprehensively analyzed by attenuated total reflectance Fourier transform infrared spectroscopy (ATR‐FTIR), proton nuclear magnetic resonance spectroscopy (1H NMR), dynamic light scattering (DLS), and scanning electron microscopy (SEM).