A highly adhesive and thermally stable copolyimide (P84) that is soluble in organic solvents is newly applied to silicon (Si) anodes for high energy density lithium-ion batteries. The Si anodes with the P84 binder deliver not only a little higher initial discharge capacity (2392 mAh g–1), but also fairly improved Coulombic efficiency (71.2%) compared with the Si anode using conventional polyvinylidene fluoride binder (2148 mAh g–1 and 61.2%, respectively), even though P84 is reduced irreversibly during the first charging process. This reduction behavior of P84 was systematically confirmed by cyclic voltammetry and Fourier-transform infrared analysis in attenuated total reflection mode of the Si anodes at differently charged voltages. The Si anode with P84 also shows ultrastable long-term cycle performance of 1313 mAh g–1 after 300 cycles at 1.2 A g–1 and 25 °C. From the morphological analysis on the basis of scanning electron microscopy and optical images and of the electrode adhesion properties determined by surface and interfacial cutting analysis system and peel tests, it was found that the P84 binder functions well and maintains the mechanical integrity of Si anodes during hundreds of cycles. As a result, when the loading level of the Si anode is increased from 0.2 to 0.6 mg cm–2, which is a commercially acceptable level, the Si anode could deliver 647 mAh g–1 until the 300th cycle, which is still two times higher than the theoretical capacity of graphite at 372 mAh g–1.