The disposal of end-of-life printed circuit boards (PCBs) comprising cross-linked brominated epoxy resins, glass fiber, and metals has attracted considerable attention from the environmental aspect. In this study, valuable resources, especially organic material, were recovered by the effective chemical recycling of PCBs. Pulverized PCB was depolymerized by glycolysis using polyethylene glycol (PEG 200) with a molecular weight of 200 g/mol under basic conditions. The cross-linked epoxy resins were effectively decomposed into a low-molecular species by glycolysis with PEG 200, followed by the effective separation of the metals and glass fibers from organic materials. The organic material was modified into recycled polyol with an appropriate viscosity and a hydroxyl value for rigid polyurethane foams (RPUFs) by the Mannich reaction and the addition polymerization of propylene oxide. RPUFs prepared using the recycled polyol exhibited superior thermal and mechanical properties as well as thermal insulation properties compared to conventional RPUFs, indicating that the recycled polyol obtained from the used PCBs can be valuable as RPUF raw materials for heat insulation.