The commercialization of high capacity silicon (3579 mAh g^-1, based on Li₁₅Si₄) is limited by the large volume change of silicon during lithiation and de-lithiation, resulting in poor cycling performance. The choice of polymeric binders is critical to the electrochemical performance of silicon based electrodes. It is known that the cyclability of silicon electrodes can be much enhanced when using carboxymethyl cellulose (CMC), sodium alginate, Nafion as binders, instead of the conventional polyvinylidene fluoride (PVDF) binder. This work focuses on a comprehensive study of the binding mechanisms of these binders for silicon electrodes. Instrumented nanoindentation is used to measure Young’s modulus, hardness, and viscoelastic behavior of these polymeric binders when the binders are either dry or immersed in the organic electrolyte. Together with characterization tools, such as Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS), the role of the mechanical behavior of binders and the interaction between polymeric binders and silicon will be reported.