Methyl propionate (MP) and methyl methacrylate (MMA) are considered as industrially important precursors upon large-scale acrylic plastic production. The existing industrial synthetic protocols of these precursors utilize expensive catalysts accompanied with toxic and explosive gases such as carbon monoxide, ethylene and hydrogen. Herein, we for the first time report highly selective, catalyst-free and room temperature synthesis of MP and MMA precursors through organic superbase involved reversible CO2 capture approach. In short, initially equimolar mixture of organic superbase 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) and methanol were reversibly reacted with molecular CO2 and the obtained switchable ionic liquid, [DBUH][MeCO3] further reacted with an equivalent amount of propionic anhydride or methacrylic anhydride to form MP or MMA, respectively. These reactions were accomplished in different solvents such as DMSO and methanol whereupon, in case of methanol, separation of reaction products occurs from in-situ formed DBU derivatives such as [DBU][propionate] or [DBU][methacrylate]. In case of both MP and MMA synthesis, after use of methanol as a solvent, good recovery of alcoholic solution of esters were achieved where 85% and 92% yields of MP and MMA were obtained, respectively.The molecular DBU was recovered using NaCl saturated alkaline solution. Further, the recovered MMA with methanol was polymerised to poly-MMA using a benzoyl peroxide induced free radical polymerisation process. The synthesis and separation of MP or MMA as well as recovery of DBU was monitored by NMR analysis. Hence, unlike DMSO, methanol not only performed as a regent in CO2 capture and as a solvent media in MP, MMA and poly-MMA synthesis but also assisted in the recovery of DBU from the reaction mixture. Most importantly, here we represented a more efficient, safer and single solvent based alternative synthetic approach for the synthesis of acrylic plastic precursors MP or MMA compared to existing industrial methods. Also, no toxic or expensive catalysts were required.