The rate capability of a Li4Ti5O12 (LTO)-based anode in a lithium ion battery can be easily improved by electron beam (EB) irradiation without the need for complicated synthetic procedures. The electrode prepared with EB-irradiated LTO at a 50 kGy dose has an enhanced rate capability while retaining a discharge capacity of 100 mAh g−1, even at the 20 C-rate. The effect of EB irradiation on the properties of the anode materials (i.e., LTO, poly(vinylidene fluoride) (PVDF), super P carbon) is examined in detail through systematic experiments. Both LTO and PVDF are affected by EB irradiation and dependent on the exposed electron dose, but super P is affected negligibly. EB irradiation partially reduces LTO with forming Tix+ (2 < x < 4) which is attributed to the enhanced electrical conductivity. EB irradiation causes dehydrofluorination and cross-linking in PVDF, resulting in the formation of carbon–carbon double bonds. The conjugated structure of PVDF is formed by the further dehydrofluorination during mixing with LTO via ball-milling, and this is accelerated in the presence of EB-PVDF. This conjugated structure enhances the electrical conductivity and is responsible for the improved rate capability.