The extraction and separation of platinum group metals (PGMs) from HLLW is of great value for resource recycling and the running of reprocessing plants. In this paper, the photochemical method was proposed to extract and separate PGMs (Pd, Ru) from simulated high level liquid wastes (HLLW). Pd and Ru metal were extracted from aqueous solution by photoreduction with high efficiency (reduction ratio >90%) in the presence of alcohols, which was confirmed by UV-vis spectroscopy, XRD, XPS and TEM analysis. The effects of various parameters such as exposure wavelength, reducing agents, Cl- and pH value were investigated to optimize the photoreaction. The highly efficient extraction and separation of Pd or/and Ru metal from their mixture with lanthanide (Nd) by selective photoreduction was realized. The results suggest that the photochemical method is a promising method for the efficient extraction and separation of PGMs from HLLW. (C) 2017 Elsevier B.V. All rights reserved.