The effects of molecular structures of the compatibilizers and blending sequences on the morphology and properties of the immiscible poly(L-lactide)/acrylonitrile-butadiene-styrene (PLLA/ABS) blend are investigated herein. The comb-like polymers (RC), which are constituted by a poly(methyl methacrylate) (PMMA) backbone and side chains and a few epoxy groups distributed randomly along the backbone, are found to be better compatibilizers for improving the morphology and mechanical properties of the PLLA/ABS blend, compared to linear polymers (RL) constituted by a PMMA backbone and epoxy groups along the backbone. In addition, the blending sequence, which dictates the extent of grafting reaction between carboxyl end groups of PLLA and epoxy groups in the RL and RC compatibilizers, is found to influence the diffusion and location of the in situ formed RL-g-PLLA and RC-g-PLLA polymers in the blend system. By blending RL or RC polymers with ABS phase firstly, the epoxy groups are diluted by ABS phase; thus, during the second step, blending with PLLA phase, lightly grafted polymers are formed. This method is found to be the best sequence to compatibilize the PLLA/ABS system. When the PLLA phase is mixed with the compatibilizers firstly, the highly grafted polymers are prone to be trapped in the PLLA phase, because the PMMA segments are shielded by the densely grafted PLLA segments from interacting efficiently with the ABS phase, and thus the morphology and mechanical properties of the blend deteriorate accordingly.