In this study, an Al-Si-Ti multilayer thin film structure is designed as the anode of a lithium ion battery. The novel structure restricts the expansion of Si during charge-discharge, and its battery capacity can reach 1112 mA h g−1 after a 100-cycle charge-charging test under a 0.2 C charge-discharge rate without annealing. Notably, after a 200 °C vacuum annealing process, the cyclic capacity of the anode rises to 1208 mA h g−1 through crystallization of the Al and Ti buffer layer. However, its thermal diffusion behavior in the Al/Si or Ti/Si interfaces seriously reduces the performance and restricts the expansion of Si. The electrically induced crystallization (EIC) process not only performs crystallization but also controls the interfacial stability, after which its capacity can obviously improve to 1602 mA h g−1 after 100 cycles. Using EIC, the electron flow drives the Cu and Al atoms to endow the Si matrix with doping properties and further increases the electron conductivity of the anode. This result demonstrates that the EIC process is a suitable post-treatment process for multilayer anodes and provides a reference for future battery designs.