Lithium-ion batteries (LIBs) have drawn significant attention in the research field because of the growing demand for energy consumption and utilization in portable electronic devices, the e-mobility revolution, grid-scale energy storage, and military and aerospace applications. Current research is focused on the discovery of anode materials for LIBs to fulfill the increasing need for materials with high energy densities. In this study, we developed an anode material composed of a tetrabenzimidazole aluminum phthalocyanine poly(AlTBImPc) complex with 10 wt % single-walled carbon nanotubes (SWCNTs). As a potential anode material, it offers unique structural properties and attractive electrochemical characteristics, which provide good ionic conductivity, cycle stability, and excellent coulombic efficiency. Numerous physicochemical techniques were used to comprehensively examine the structural characteristics of this complex. The self-assembly strategy for the 10 wt % CNT-encased poly(AlTBImPc) composite improved its electrochemical performance. In a half-cell operating at 0.1 A g −1 , poly(AlTBImPc)/SWCNT anodes delivered initial capacities of 1464 and 1130.56 mA g −1 after 100 cycles and an impressive rate capability of 826 mA g −1 at 0.5 A g −1 , which outperformed its counterparts (poly(AlTBImPc) and poly(AlTBImPc)/MWCNT). The enhanced performance of the poly(AlTBImPc)/SWCNT was associated with improved Li-ion kinetics, reduced volume change, high electrical conductivity, and mechanical flexibility. The advantages of poly(AlTBImPc)/SWCNTs include high energy density, sustainability, affordability, safety, and environmental friendliness.