Through pyrolysis under a supercritical water (SCW) environment, the demetallization of Tsingtao vacuum residuum (VR) and Tahe atmospheric residuum (AR) with a total vanadium and nickel content above 300 ppm was studied. By introducing SCW, pyrolysis of heavy oil can be carried out in an emulsion structure in which heavy fractions rich in metals are concentrated in oil droplets. A metal removal rate higher than 90% could be obtained in 2 h, which is faster than the pyrolysis under the nitrogen environment. Although the two heavy oils have similar apparent properties, Tsingtao VR is characterized by the metal enrichment in the heaviest asphaltenes and the higher condensation activity of asphaltenes. Because of the preferential condensation of heavy fractions rich in metals, the liquid product yield of Tsingtao VR could be 15 wt % higher than that of Tahe AR at the metal removal rate of 70% to 90%.