Waste electrical and electronic equipment is rapidly increasing worldwide, resulting in a large quantity of waste printed circuit boards (WPCBs). There is a great challenge on how to efficiently separate mixed metals in WPCBs, which consists of more than 10 elements including hazardous Cr, Pb and Cd. In this work, based on atomic interactions, a method of liquid-liquid hierarchical separation is developed to separate the mixed metals dissociated from the pyrolyzed WPCBs of mobile phones. The hierarchical separation of L -> LFe-rich + L-cu,L-Pb-rich, L-Cu,L-Pb-rich -> Lcu-rich + Lpb-rich and Lpb-rich -> SCu-dendritical + Lpb-rich produces four immiscible Fe-rich, Cu-rich, Cu-dendritical and Pb-rich substances. The separation rate between these substances can reach more than 96% in a super-gravity field of G = 1000g. Other metals selectively distribute in the four substances. The Fe-rich substance collects Cr, Co, Ni and Si. Almost all of Au and Ag are trapped in the Cu-rich and Cu-dendritical substances. The low-melting-point metals, i.e. Bi, Cd, In and Sn, are located in the Pb-rich substance. This work provides a green shortcut for efficiently separating and recycling overall metals in WPCBs.