Biopolymers are abundant, renewable, and biodegradable resources. However, bio-based materials often require toughening additives, like (co)polymers or small plasticizing molecules. Plasticization is monitored via the glass transition temperature versus diluent content. To describe this, several thermodynamic models exist; nevertheless, most expressions are phenomenological and lead to over-parametrization. They also fail to describe the influence of sample history and the degree of miscibility via structure-property relationships. We propose a new model to deal with semi-compatible systems: the generalized mean model, which can classify diluent segregation or partitioning. When the constant kGM is below unity, the addition of plasticizers has hardly any effect, and in some cases, even anti-plasticization is observed. On the other hand, when the kGM is above unity, the system is highly plasticized even for a small addition of the plasticizer compound, which indicates that the plasticizer locally has a higher concentration. To showcase the model, we studied Na-alginate films with increasing sizes of sugar alcohols. Our kGM analysis showed that blends have properties that depend on specific polymer interactions and morphological size effects. Finally, we also modeled other plasticized (bio)polymer systems from the literature, concluding that they all tend to have a heterogeneous nature.