Electrolytic manganese dioxide (EMD) recovered from a simulated leaching solution of spent alkaline batteries using a modified cyclone cell is tested as a cathode material for Li secondary batteries. An EMD/C(Super P) composite heat-treated at 400°C after high-energy mechanical milling shows better electrochemical performance than that of pure EMD in terms of cycleability and capacity fading. The electrochemical characteristics of the EMD/C(Super P) composite are investigated by various analytical techniques. The irreversible capacity during the first cycle is mainly due to the formation of a Li2MnO3 phase. The carbon composite also retards the dissolution of Mn during cycling.