Herein, we report the use of the use of non-ionic deep eutectic solvents (ni-DESs) as porogens in polymer synthesis. Three ni-DES systems, acetamide-N-methylacetamide (AA-NMA), N-methylacetamide-N-methylurea (NMA-NMU) and N-methylacetamide-N,N′-dimethylurea (NMA-NN'DMU), were deployed in the synthesis of a series of cross-linked copolymer monoliths comprised of a functional monomer, methacrylic acid (MAA) or hydroxyethylmethacrylate (HEMA), and a cross-linking monomer, ethylene glycol dimethylacrylate (EGDMA) or divinylbenzene (DVB) or 1,4-bis(acryloyl)piperazine (BAP). Polymers were synthesized under thermally initiated conditions with 2,2′-azobis(2-methylpropionitrile) (AIBN) or 2,2′-azobis(2-amidinopropane) dihydrochloride (ABAH) as an initiator. The resulting polymer monoliths were ground and sieved to yield particles of 63–125 μm. Corresponding polymers prepared in conventional porogens, acetonitrile, toluene and water were synthesized to serve as controls. The influence of the respective ni-DESs on polymer morphologies was examined by Brunauer–Emmett–Teller (BET) N₂-adsorption, Fourier transform infrared spectroscopy (FT-IR), elemental analysis, scanning electron microscopy (SEM) and zeta potential measurements. The materials displayed surface areas, pore volumes and pore diameters of 115–532 m² g⁻¹, 0.1–1.4 cm³ g⁻¹ and 5.2–12.5 nm, generally comparable with those of polymers obtained using conventional solvents, thus presenting these ni-DESs as viable alternatives to conventional organic solvents. The post-polymerization recovery of the ni-DESs (>80%) was demonstrated, highlighting the potential for using these novel liquids as alternatives to conventional, and often more expensive, toxic, flammable or volatile solvents in polymer synthesis.