application. [ 1,2 ] However, bulk or microsize red P materials suffer from dramatic capacity reduction and poor cyclability with continued usage [ 1h ] due to their electronic insulation (≈10 −14 S cm −1 ) [ 1f ] and irreversible reaction related to the pulverization of particles, [ 1c , 3 ] which is caused by drastic volume change (>300%) [ 1h ] during cycling process. In light of this, black P is an alternative electrode material for high-performance LIB application due to its high electrical conductivity (≈10 2 S cm −1 ) [ 1h , 4 ] and fast kinetics during the Li + intercalating process. [ 4a,c ] Nevertheless, the traditional high-pressure method (>1 GPa, Scheme 1 a) through a pressure-induced structure-change mechanism is extremely diffi cult as it relies on specifi cally designed apparatus under controlled temperature (≥200 °C). [ 4c , 5 ] Recently, a facile mineralizer-assisted gas-phase transformation method was developed to produce large-size bulk black P. [ 6 ] However, the resultant particles by the above approaches are more than tens of micrometers in size, [ 5a , 6 ] which renders them unsuitable for high-rate LIB application. Therefore, material nanostructuring and engineering of the red/black P toward the improvement of electrical/ionic conductivity and the alleviation of volume expansion is desired for high-rate LIBs. [ 7 ] To this end, conductive confi gurations of nanostructured phosphorus materials (amorphous or red P, P-C composites, and metal phosphide, Scheme 1 a) [ 1d,e , 2e , 8 ] with buffering of volume change are widely explored through mechanical approaches (e.g., hand-grinding, mechanical milling, etc., as shown in Table S1, Supporting Information). [ 1f , 2a , 3,9 ] Furthermore, an emerging high energy mechanical milling by generating the suffi cient pressure (≈6 GPa) and temperature, [ 1c ] (Scheme 1 a), could even produce the most thermodynamically stable black P or composites with the particles size down to subhundred nanometer, which showed improved LIB performance. [ 1c,h ] Impressively, these nanostructured phosphorus or its composites [ 1d,e , 8 ] could realize high capacity (>1000 mAh g −1 ) as well as long-cycling life (>100 cycles) for LIBs. However, these top-down mechanical approaches remain diffi cult with respect to obtaining largescale uniform distribution of phosphorus nanostructures, as Phosphorus-based materials are promising for high-performance lithium-ion battery (LIB) applications due to their high theoretical specifi c capacity. Currently, the existing physical methods render great diffi culty toward rational engineering on the nanostructural phosphorus or its composites, thus limiting its high-rate LIB applications. For the fi rst time, a sublimation-induced synthesis of phosphorus-based composite nanosheets by a chemistry-based solvothermal reaction is reported. Its formation mechanism involves solidvapor-solid transformation driven by continuous vaporization-condensation process, as well as subsequent bottom-up assembly growth. The proof-o...