The objective of this work deals with the realization of high O2-barrier blown films based on novel biodegradable blends of Polybutylene succinate (PBS) and Poly-vinyl alcohol (PVOH) for food packaging applications. Blends at different PBS/PVOH weight ratios (100/0, 80/20, 60/40, 0/100 wt%) were produced and their processability and miscibility was preliminary assessed by means of dynamic shear rheological tests. Afterwards, blown films were realized and then characterized in terms of chemical properties and oxygen barrier performance. The results revealed that, although immiscible, polymers in the blend show some degree of interaction. Moreover, as the concentration of PVOH in the films increased, a significant decrease in oxygen permeability was obtained with respect to the neat PBS film, up to 42% for the PBS/PVOH 60/40 sample. The findings of this study highlighted the promising perspectives of these films as sustainable packaging for sensitive foods with high O2-barrier requirements.