The printing of polyester (PET) fabrics using binders and disperse dyes is an environmentally less harmful technique due to the exclusion of water‐intensive washing processes. Unfortunately, the conventional polyacrylate (PA) binders are inapplicable for this printing technique as the high PA‐disperse dye compatibility restrains the migration of disperse dye molecules from binder films into PET fabrics. Herein, we demonstrate a rational design and synthesis of novel PA binders by copolymerizing fluorosilicone monomers with multi‐vinyl groups for the sustainable printing of PET fabrics. The incorporated fluorosilicone functionalities significantly decrease the solubility parameter of PA, facilitating the dye molecules migration toward PET fabrics. Meanwhile, the crosslink structure formed via vinyl groups restrains the migration of polymer chains and thus allows for the anchor of F/Si segments, enabling the continuous migration of disperse dyes. As a result, both the utilization ratio of disperse dyes and the color yield and fastness of printed PET fabrics are substantially improved. Moreover, the washing‐free printing process using the developed binder can reduce 73% of water consumption, 74% of energy input, and 100% of wastewater discharge over the traditional printing process. Our study may provide insights into rational design of binders for the sustainable printing of PET fabrics.