Herein,　a　heterostructural　hexagonal@tetragonal　GeO2　(HT-GeO2)　composite　has　been　designed　based　on　density　functional　theory　(DFT)　calculations　and　synthesized　via　an　acidic-heating　route　dealt　with　rapid　cooling,　where　the　inner　hexagonal　GeO2　(H-GeO2)　phase　is　covered　by　a　porous　layer　of　tetragonal　GeO2　(T-GeO2)　owing　to　HF　etching.　Interestingly,　the　HT-GeO2　electrode　has　a　self-optimizing　effect　in　lithium　storage　induced　by　heterointerface　regulation,　where　the　porous　T-GeO2　layer　on　the　surface　of　HT-GeO2　can　act　as　not　only　a　Li+/electron　conducting　layer,　but　also　a　buffer　layer,　while　the　inner　H-GeO2　phase　can　react　preferentially　with　Li　ions　owing　to　lower　intercalation　energy,　which　is　confirmed　by　operando　XRD　measurement　contributing　to　thorough　lithiation　for　HT-GeO2.　Moreover,　the　heterointerface　can　enhance　the　pseudocapacitance　effect,　which　can　boost　the　Li　storage　and　accelerate　the　discharge-charge　process.　As　a　result,　a　large　capacity　of　984　mAh　g(-1)　after　500　cycles　at　2　A　g(-1)　and　a　capacity　of　430　mAh　g(-1)　at　a　high　current　density　of　20　A　g(-1)　are　delivered.　This　work　provides　an　easy　and　efficient　way　to　improve　the　cycling　stability　of　the　GeO2　anode,　and　the　T-GeO2　phase　would　be　a　novel　anode　material　in　energy　storage　devices.