An understanding of structural features of plasticizers that govern their migration behaviour out of the polymer matrix is important to improving the permanence of blend properties and limit environmental and toxic contamination. Our group has previously shown that succinate diesters with varying alkyl chain lengths can function effectively as plasticizers in poly(vinyl chloride) (PVC) blends. They are readily biodegraded into innocuous metabolites and display comparable aqueous leaching rates to commercial plasticizer di(2-ethylhexyl) phthalate (DEHP). In this work, this family of compounds was expanded upon further while the influence of branching on plasticizer effectiveness and migration behavior of succinate plasticizers blended with PVC was evaluated. An increase of branching led to a decrease in migration of the plasticizers into both hexanes and vegetable oil medias. Additionally, a quantitative 1H-NMR method was used to identify plasticizer concentration in the leachates and compared to the ASTM gravimetric standard testing protocol. Overall, it was found that the quantitative 1H-NMR method proved to be a more direct method to assess leaching. In comparison to DEHP and alternative green plasticizer diheptyl succinate (DHPS), all the branched species displayed superior migration resistance into hexanes (i.e., two to ten-fold improvement). The glass transition temperatures, surface hardness, and stress at break indicated that the plasticizers comprised of up to three branches functioned as well as, or better than, DEHP and DHPS. However, there was a marked decrease in plasticizer efficiency with compounds comprised of four or more branches as they produced stiffer blends with inferior mechanical properties.