As an intermetallic material, Bi2Te3 possesses great potential in lithium-ion batteries due to its attractive layered structure, intrinsic excellent conductivity and impressive theoretical specific capacity. However, the phase decomposition and the huge volume variation leading to rapid capacity fading hinder the further application of Bi2Te3 in lithium-ion batteries. In this study, two dimensional Bi2Te3 encapsulated in cobalt polyphthalocyanine (CoPPc) is synthesized by a facile recrystallization method, and its electrochemical properties and lithium storage mechanism are comprehensively studied. The Bi2Te3@CoPPc electrodes exhibit outstanding cycling stability with a specific capacity of 551.9 mAh g?1 at 100 mA g?1 and 628.5 mAh g?1 at 500 mA g?1 after 500 cycles, benefiting from the configured composite layered structure and the amiable interaction of Bi2Te3 and CoPPc. Our experimental and theoretic results demonstrate that the electron redistribution induced by the incorporation of CoPPc with charge accumulation around Bi2Te3 and low potential region around Co efficiently facilitates the fast lithium-ion transportation resulting in outstanding rate performance. Our explorative strategy of electron redistribution proposes a new avenue to enhance the catalysis activity and durability of alloy anodes in metal-ion batteries.