Taken together, this study introduces a new potential polymer excipient enabling amorphous blends with high levels of amorphous drugs for drug delivery applications. Due to the living cationic ring-opening polymerisation, the polymer can be easily modulated depending on the requirements. In combination with MEW, highly porous fibrous scaffolds can be fabricated without the need of a toxic solvent and with high precision of fiber placement offering a wide range of designs for further applications, even beyond sublingual drug delivery approaches.