Poly(acrylic acid) (PAA) based binders have been widely used for the high capacity silicon anodes of lithium-ion batteries. While numerous promising progress has been reported, there is no general guideline for choosing the right PAA binders for optimized cycling performance. In this report, aiming to optimize the cycling performance of the Si/graphite composite anodes (15 wt% Si), we systemically investigated a series of PAA binders by validating their molecular weights (MWs) and correlating them to the cycling performance of the anodes fabricated with such binders. The gel permeation chromatography (GPC) was used to validate the MWs of six PAA binders (PAA1 to PAA6). Those binders then underwent a series of characterizations, including rheology study, half-cell cycling, scanning electron microscope (SEM), and Fourier-transform infrared spectroscopy (FTIR). It is observed that the MWs of PAA binders not only affected the viscosities of the binder solutions but also impacted the cycling performance, possibly due to the cohesion changes. A range of 24–150 kDa is found to be optimal for minimizing the rate and extent of capacity fade and maintaining the cohesion in the electrode matrix despite the dramatic volumetric changes due to Si alloying.