Vinyl-functionalized graphene oxide (VGO) was used as a reactive compatibilizer to prepare poly(lactic acid)/polybutylene adipate-co-terephthalate (PLA/PBAT) blends. The linear rheological and scanning electron microscopy results confirmed that the VGO nanosheets were quite efficient in compatibilizing PLA/PBAT blends. The size of the PBAT dispersed phase was remarkably decreased in the presence of VGO nanosheets. Moreover, the VGO nanosheets exhibited strong nucleating effects on the crystallization process of PLA. The crystallinity of PLA component in the compatibilized blend with various VGO nanosheets was higher than 40%, upon the cooling rate of 20 °C/min. The prepared PLA/PBAT pellets were applied to 3D printing, using a self-developed screw-based 3D printer. The results showed that all the prepared PLA/PBAT blend pellets can be 3D printed successfully. The notched Izod impact test results showed that, in the presence of VGO, an increase of at least 142% in impact strength was achieved for PLA/PBAT blend. This could be attributed to the compatibilizing effect of the VGO nanosheets. Thus, this work provides a novel way to prepare tough PLA-based materials for 3D printing.