A poly(styrene-ran-methyl acrylate) (S-MA) (75/25 mol/mol), synthesized by surfactant-free emulsion copolymerization, was used as a compatibilizer for polystyrene-b-polybutadiene-b-polystyrene (SBS)-toughened polylactide (PLA) blends. Upon compatibilization, the blends exhibited a refined dispersed-phase morphology, a decreased crystallinity with an increase in their amorphous interphase, improved thermal stability possibly from the thicker, stronger interfaces insusceptible to thermal energy, a convergence of the maximum decomposition-rate temperatures, enhanced magnitude of complex viscosity, dynamic storage and loss moduli, a reduced ramification degree in the high-frequency terminal region of the Han plot, and an increased semicircle radius in the Cole-Cole plot due to the prolonged chain segmental relaxation times from increases in the thickness and chain entanglement degree of the interphase. When increasing the S-MA content from 0 to 3.0 wt %, the tensile properties of the blends improved considerably until 1.0 wt %, above which they then increased insignificantly, whereas the impact strength was maximized at an optimum S-MA content of similar to 1.0 wt %, hypothetically due to balanced effects of the medium-size SBS particles on the stabilization of preexisting crazes and the initiation of new crazes in the PLA matrix. These observations confirm that S-MA, a random copolymer first synthesized in our laboratory, acted as an effective compatibilizer for the PLA/SBS blends.