In this work,azobenzene mesogen-containing tin thiolates have been synthesized,which possess ordered lamellar structures persistent to higher temperature and serve as liquid crystalline precursors.Based on the preorganized tin thiolate precursors,Sn S nanocrystals encapsulated with in-situ N-doped carbon layer have been achieved through a simple solventless pyrolysis process with the azobenzene mesogenic thiolate precursor served as Sn,S,N,and C sources simultaneously.Thus prepared nanocomposite materials as anode of lithium ion batteries present a large specific capacity of 604.6 m Ah·g~(-1)at a current density of 100 m A·g~(-1),keeping a high capacity retention up to 96% after 80 cycles,and display high rate capability due to the synergistic effect of well-dispersed Sn S nanocrystals and N-doped carbon layer.Such encouraging results shed a light on the controlled preparation of advanced nanocomposites based on liquid crystalline metallomesogen precursors and may boost their novel intriguing applications. In this work, azobenzene mesogen-containing tin thiolates have been synthesized, which possess ordered lamellar structures persistent to higher temperature and serve as liquid crystalline precursors. Based on the preorganized tin thiolate precursors, Sn S nanocrystals encapsulated with in-situ N-doped carbon layer have been achieved by a simple solventless pyrolysis process with the azobenzene mesogenic thiolate precursor served as Sn, S, N, and C sources. Thus prepared nanocomposite materials as anode of lithium ion batteries present a large specific capacity of 604.6 m Ah · g ~ (-1) at a current density of 100 m A · g -1, keeping a high capacity retention up to 96% after 80 cycles, and display high rate capability due to the synergistic effect of well-dispersed Sn S nanocrystals and N-doped carbon layers. Suu encouraging results shed a light on the controlled preparation of advanced nanocomposites based on liquid crystalline metallomesogen precursors and may boost their novel i ntriguing applications.