Abstract Silicon is attracting enormous attention due to its theoretical capacity of 4200 mAh g −1 as an anode for Li‐ion batteries (LIBs). It is of fundamental importance and challenge to develop low‐temperature reaction route to controllably synthesize Si/Ti 3 C 2 MXene LIBs anodes. Herein, a novel and efficient strategy integrating in situ orthosilicate hydrolysis and a low‐temperature reduction process to synthesize Si/Ti 3 C 2 MXene composites is reported. The hydrolysis of tetraethyl orthosilicate leads to homogenous nucleation and growth of SiO 2 nanoparticles on the surface of Ti 3 C 2 MXene. Subsequently, SiO 2 nanoparticles are reduced to Si via a low‐temperature (200 °C) reduction route. Importantly, Ti 3 C 2 MXene not only provides fast transfer channels for Li + and electrons, but also relieves volume expansion of Si during cycling. Moreover, the characteristics of excellent pseudocapacitive performance and high conductivity of Ti 3 C 2 MXene can synergistically contribute to the enhancement of energy storage performance. As expected, Ti 3 C 2 /Si anode exhibits an outstanding specific capacity of 1849 mAh g −1 at 100 mA g −1 , even retaining 956 mAh g −1 at 1 A g −1 . The low‐temperature synthetic route to Si/Ti 3 C 2 MXene electrodes and involved battery‐capacitive dual‐model energy storage mechanism has potential in the design of novel high‐performance electrodes for energy storage devices.