High boiling point phenolic reactive solvents likep-cresol could play a key role in improving the synthesis of aromatic polyesters with a high content of secondary diols such as isosorbide. Previously, our group showed that this method significantly improves the synthesis of poly(isosorbide succinate). In this work, terephthalic acid and 2,5-furandicarboxylic acid were used as building blocks for the synthesis of highTgpolyesters with high isosorbide content (>30 mol% of diols) and high molecular weight (Mn> 24 kg mol−1). A number of reactive and non-reactive solvents were tested in this work, and the results clearly point to a significant improvement when using reactive solvents, in terms of molecular weight and polycondensation time, especially for the case ofp-cresol. The synthesis method was successfully scaled to 1 kg, showing promise for production at industrial scale. A method to remove these solvents (including end groups) from the polymers, which uses small excesses of isosorbide (1.5–3.0%) in the feed, is also presented.