To investigate the correlation between the molecular weight of the polymeric binder in Li-ion battery electrodes and their adhesion properties, polyvinylidene fluoride (PVdF) with three different molecular weights of 500,000, 630,000, and 1,000,000 are selected for LiCoO2 electrode fabrication. Using a surface and interfacial cutting analysis system, it is observed that, as the molecular weight of the PVdF increases, the adhesion strength not only in the electrode composite, but also at the electrode/current collector interface increases. This enhancement can be attributed to the increased polymeric chain entanglement and higher crystallinity of PVdF with higher molecular weight, which is confirmed using a microfluidic viscometer and differential scanning calorimeter, respectively. In summary, regardless of slightly higher electrode resistance, the LiCoO2 electrode with a PVdF binder of high molecular weight shows better electrochemical performance during cycling test even at 60 °C due to its stable mechanical integrity.