Three　types　of　new-structured　phosphorized　tin　microspheres　(Sn-P),　phosphorized　tin　microsphere-carbon　(Sn-P-C),　and　phosphorized　tin　nanoparticles　embedded　in　interconnected　porous　carbon　microspheres　(Sn-P@PCMs)　were　prepared　through　a　carbothennal　reduction-assisted　phosphorization　strategy.　The　characterization　of　the　formation　mechanism　and　microstructure　of　Sn-P,　Sn-P-C,　and　Sn-P@PCMs　composites　demonstrated　that　the　controllable　evaporation　of　coordinated　phosphorus　in　the　thermally　unstable　tin　phosphide　intermediate　by　accurate　thermal　treatment　contributed　to　the　formation　of　a　ca.　3　wt　%　P-doped　metallic　tin　structure　featuring　a　nonstoichiometric　SnxPy　(y/x　=　0.2)　core,　a　Sn-rich　phosphorized　metallic　(y/x　=　0.05)　shell,　and　an　increased　phosphorus　concentration　from　the　outer　surface　to　the　inner　core.　The　as-prepared　phosphorized　tin-based　composites　were　applied　as　counter　electrode　materials　for　dye-sensitized　solar　cells　(DSSCs),　in　which　the　Sn-P-C　counter　electrode　exhibited　the　lowest　charge　transfer　resistance　of　3.47　Omega　and　the　assembled　DSSCs　delivered　an　optimum　power　conversion　efficiency　of　8.59%,　superior　to　those　of　Pt-based　cells　(6.78　Omega　and　7.46%,　respectively).　The　unique　bifunctional　structure　of　the　SnxPy　conductive　core　coupled　with　the　phosphorized　metallic　Sn　delta+　(0　＜　sigma　＜　0.6)　electrocatalytic　shell　accounts　for　its　excellent　electrocatalytic　activity　and　electrical　conductivity.　In　addition,　the　phosphorized　tin-based　composites　were　utilized　as　potential　anodic　material　for　lithium-ion　batteries,　in　which　the　Sn-P@PCM5　electrode　showed　a　specific　capacity　of　743　mAh　g(-1)　at　0.1C　after　400　cycles　and　435　mAh　g(-1)　at　5C　after　30　cycles.　The　superior　Li-ion　storage,　cydability,　and　rate　performance　of　Sn-P@PCMs　could　be　attributed　to　the　incorporation　of　Sn-P　nanopartides　into　interconnected　porous　carbon　microspheres　that　effectively　buffered　the　large　volumetric　change　and　enhanced　the　electronic-ionic　conductivity　during　the　lithiation　and　delithiation　process.