Silicon (Si) is a promising anode material for next-generation lithium ion batteries (LIBs) because of its high capacity of 4,200 mAh/g (Li4.4Si phase). However, the large volume expansion of Si during lithiation leads to electrical failure of electrode and rapid capacity decrease. Generally, a binder is homogeneously mixed with active materials to maintain electrical contact, so that Si needs a particular binding system due to its large volume expansion. Polyvinyl alcohol (PVA) is known to form a hydrogen bond with partially hydrolyzed silicon oxide layer on Si nanoparticles. However, the decrease of its cohesiveness followed by the repeated volume change of Si still remains unsolved. To overcome this problem, we have introduced the electrospinning method to weave active materials in a stable nanofibrous PVA structure, where stresses from the large volume change of Si can be contained. We have confirmed that the capacity retention of Si-based LIBs using electrospun PVA matrix is higher compared to the conservative method (only dissolving in the slurry); the 25th cycle capacity retention ratio based on the 2nd cycle was 37% for the electrode with electrospun PVA matrix, compared to 27% and 8% for the electrodes with PVdF and PVA binders.