Here,　a　case　of　bilayer　heterojunction　Pd-containing　polyoxotungstate　(POW),　connecting　a　Te3Pd3　ring　and　an　Anderson-like　TeW6　cluster,　has　been　synthesized.　The　Anderson-like　cluster　is　the　first　example　in　POW.　The　coordination　of　Pd　in　the　ring　with　the　S　atom　on　the　sulfo　group　breaks　the　traditional　coordination　configuration　of　Pd　and　O　in　polyoxometalates　(POMs),　enriching　the　structural　types　of　Pd-containing　POMs.　In　addition,　the　hybrid　bilayer　heterojunction　structure　at　the　molecular　level　not　only　provides　high　thermal　stability　but　also　results　in　spatial　arrangement　anisotropy,　leading　to　up　to　five　times　the　anisotropic　proton　conductivity.　©　2024　American　Chemical　Society.