Starch nanoparticles (SNP) were modified with synthetic polymers using the "grafting to" approach and nitroxide-mediated polymerization. SG1-capped poly(methyl methacrylate-co-styrene) (P(MMA-co-S)) copolymers with low dispersity and high degree of livingness were first synthesized in bulk. These macro-alkoxyamines were then grafted to vinyl benzyl-functionalized SNP to obtain biosynthetic hybrids. The grafted materials, SNP-g-P(MMA-co-S), were characterized by H-1 NMR, FTIR, TGA, and elemental analysis. The total amount of grafted polymer and the grafting efficiency were evaluated for different molecular weights (5870-12150 g-mol(-1)) of the grafted polymer, the polymer addition approach (batch or semibatch) and the initial polymer loading (2.5, 5, or 10 g polymer/g SNP). The proposed approach presented in this work to graft modify SNP allows for a precise surface modification of the nanoparticles, while permitting that the final properties of the resulting biohybrid to be tunable according to the choice of polymer grafted.