Abstract An alternative way has been proposed for the PVC-containing medical wastes valorization by co-hydrothermal carbonization (HTC) with lignocellulosic biomass. The organic-Cl in PVC can be converted to the inorganic-Cl via hydrolysis, defunctionalization, recondensation, and aromatization in the HTC process. Followed by the washing process with the condensed water, the inorganic-Cl with high water-solubility could be removed from the solid products (i.e. hydrochar). Lignin as a biomass component can significantly improve the dechlorination efficiency of PVC in the HTC process. Here, the dechlorination performance of lignocellulosic components is given as the following order: lignin > cellulose > hemicellulose. In addition, lignin can adjust the particle sizes of solid products by inhibiting the agglomeration in the order of lignin > hemicellulose > cellulose. In the pilot-scale HTC process, the addition of woodchips improves the dechlorination efficiency of hospital wastes (HW). The hydrochar particles with low-chlorine content and higher heating value could be used as a clean coal-alternative fuel.