Paper cup composed of crude cellulose is a common waste in daily life. In this paper, hierarchical porous carbons have been successfully prepared by an initial hydrothermal treatment and subsequent activation route from abandoned paper cup, and then paper cup derived carbons are used as scaffolds to fabricate serial carbon/Se composites. The optimal composite presents unique 3D porous structure, with amorphous selenium uniformly confined into the micropores of carbon. As the cathode materials of Li-Se battery, this composite reveals an initial reversible discharge capacity of 517.2 mAh g−1 at 0.2C, and a capacity value of 431.9 mAh g−1 can be retained after 60 cycles. Even at a high rate of 4C, a capacity value of 295.8 mAh g−1 can be obtained. By comparison, the improved electrochemical performance of the optimal composite should be attributed to reasonable porous structure and effective encapsulation of amorphous selenium.