Among silicon‐based anode family for Li‐ion battery technology, SiOx, a nonstoichiometric silicon suboxide holds the potential for significant near‐term commercial impact. In this context, this study mainly focuses on demonstrating an innovative SiOx@C anode design that adopts a pre‐lithiation strategy based on in situ pyrolysis of Li‐salt of silsesquioxane trisilanolate without the need for lithium metal or active lithium compounds and creates dual carbon encapsulation of SiOC nanodomains by simply one‐step thermal treatment. This ingenious design ensures the pre‐lithiation process and pre‐lithiation material with high‐environmental stability. Moreover, phenyl‐rich organosiloxane clusters and polyacrylonitrile polymers are expected to serve as internal and external carbon source, respectively. The formation of an interpenetrating and continuous carbon matrix network would not only synergistically offer an improved electrochemical accessibility of active sites but also alleviate the volume expansion effect during cycling. As a result, this new type of anode delivered a high reversible capacity, remarkable cycle stability as well as excellent high‐rate capability. In particular, the L2‐SiOx@C material has a high initial coulomb efficienc of 80.4% and, after 500 cycles, a capacity retention as high as 97.5% at 0.5 A g−1 with a reversible specific capacity of 654.5 mA h g−1.