The microhardness of films of poly(ethylene terephthalate) (PET) and poly(ethylene naphthalene-2,6-dicarboxylate) (PEN) blends prepared by co-precipitation from solution followed by melt-pressing and quenching was determined. The miscibility, transesterification and crystallization properties of these blended films were reported previously [1]. The PET/PEN compositions chosen were 10/90, 30/70, 44/56, 60/40, 70/30 and 90/10. The microhardness of films was notably affected by the composition. It is shown that the deviation of microhardness from the additivity law of the single components depends on the time for which the blend was melt-pressed before quenching in ice water. The results are discussed in light of changes occurring from the initial two-phase structure of the single components through the one-phase structure up to the PET-co-PEN obtained by transesterification of the two components.