<p>The molecular design of bio-based plasticizers often involves a trade-off between key performance and sustainability. Herein, we propose a novel molecular design strategy that breaks this contradiction by integrating a flexible backbone derived from non-edible sources, sustainable alicyclic rigid core, and epoxy groups. A series of epoxy-functionalized cyclohexane-based ricinoleate plasticizers, epoxyacetyl ricinoleic acid cyclohexanol ester (EACHR), epoxyacetyl ricinoleic acid cyclohexanediol ester (EACHDR), and epoxyacetyl ricinoleic acid cyclohexanedimethanol ester (EACHDMR), were synthesized. When evaluated in poly(vinyl chloride) (PVC) as a demanding validation platform, the optimal plasticizer (EACHDMR) achieved comprehensive performance, which reduced the glass transition temperature (<i>T</i>_g) by 30%, increased the elongation at break by more than 50-fold, and enhanced the notched impact strength by over 35-fold compared to an unplasticized PVC sample. Importantly, EACHDMR exhibited lower migration and 20.7% higher plasticizing efficiency than the commercial benchmark dioctyl terephthalate (DOTP). This study demonstrated that by rationally integrating rigid cores, flexible fatty acid chains, and polar groups, it is possible to successfully balance performance and sustainability, providing a new design strategy for developing high-performance and sustainable alternatives to traditional plasticizers.</p>