This work addresses a novel bio-solvolysis process for the treatment of complex poly(ethylene terephthalate) (PET) waste using a biobased monoethylene glycol (BioMEG) as a depolymerization agent in order to achieve a more sustainable chemical recycling process. Five difficult-to-recycle PET waste streams, including multilayer trays, coloured bottles and postconsumer textiles, were selected for the study. After characterization and conditioning of the samples, an evaluation of the proposed bio-solvolysis process was carried out by monitoring the reaction over time to determine the degree of PET conversion (91.3–97.1%) and bis(2-hydroxyethyl) terephthalate (BHET) monomer yield (71.5–76.3%). A monomer purification process, using activated carbon (AC), was also developed to remove the colour and to reduce the metal content of the solid. By applying this purification strategy, the whiteness (L*) of the BHET greatly increased from around 60 to over 95 (L* = 100 for pure white) and the Zn content was significantly reduced from around 200 to 2 mg/kg. The chemical structure of the purified monomers was analyzed via infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC), and the composition of the samples was measured by proton nuclear magnetic resonance (¹H-NMR), proving a high purity of the monomers with a BHET content up to 99.5% in mol.