AbstractPCTA is an important copolyester that has been widely used in our daily necessities. Currently, its monomers are industrially produced from petroleum‐derived xylene. To reduce the reliance on fossil energy, we herein disclose an alternative route to access PCTA monomer (terephthalate/isophthalate=2.4/1) in 61 % overall yield using plant‐based acrylate and acetaldehyde as the feedstocks. The process includes Morita–Baylis–Hillman (MBH) reaction of acetaldehyde with acrylate, subsequent one‐step dehydration/Diels–Alder reaction with acrylate over H2SO4/SiO2 catalyst, and final Pd/C‐catalyzed dehydrogenation. Besides, when varying the final step to hydrogenation, another important monomer UNOXOL™ diol (1,4‐trans/1,4‐cis/1,3‐trans/1,3‐cis=5.2/2/2.5/1) can be produced in 67 % overall yield.