The commercialized binder carboxymethyl cellulose sodium (CMC‐Na) is considered unsuitable for micro‐sized SiOx anode as it cannot endure the large volume change to retain the conductive network during repeated charge/discharge cycles. Herein, a small amount of silicon nanoparticles (SiNPs) is added during slurry preparation process as “nano‐combs” to unfold the convoluted CMC‐Na polymer chains so that they undergo a coil‐to‐stretch transition by interaction between polar groups (e.g., –OH, –COONa) of polymer and SiNPs’ large surface. Through maximizing the utilization of binders, a uniform conductive network is constructed with increased interfacial contact with micro‐sized SiOx. As a result, the SiOx electrode with optimized (10 wt%) SiNPs addition shows significantly improved initial capacity and cycling performance. Through revisiting CMC‐Na, a currently deemed unqualified binder in SiOx anode, this work gives a brand‐new perspective on the failing mechanism of Si‐based anode materials and an improving strategy for electrode preparation.