The　Hybrid　nanoparticles　of　GeO2/C　have　been　fabricated　by　decomposition　of　open-framework　germanate　compounds　GeO2-ethylenediamine　(GeO2-EDA)　built　up　from　Ge-O　clusters,　and　delivers　a　superior　Li-storage　capacity　of　984.2　mA　h　g−1　at　a　rate　of　0.2　A　g−1.　In　addition,　a　remarkable　cycling　performance　with　a　capacity　of　891.4　mA　h　g−1　has　been　obtained　after　600　cycles　for　GeO2/C　nanocomposite　at　a　current　density　of　1　A　g−1.　Furthermore,　the　full　cell　with　a　commercial　LiFePO4　cathode　shows　a　capacity　retention　of　86%　(339.4　W　h　kg–1)　over　100　cycles.　The　brilliant　electrochemical　properties　of　GeO2/C　nanocomposite　in　terms　of　the　desirable　capacity,　outstanding　cycling　stability,　and　superb　rate　performance　is　due　to　the　following　factors:　(i)　the　electrical　conductivity　of　GeO2　has　been　enhanced　significantly　by　carbon　layer　coating;　(ii)　GeO2/C　nanocomposite　with　a　porous　structure　can　buffer　the　severe　volume　changes;　and　(iii)　GeO2　nanoparticles　can　shorten　the　diffusion　distance　of　lithium　ions.　As　a　result,　the　GeO2/C　nanocomposite　exhibited　an　excellent　electrochemical　performance　as　an　anode　in　LIBs.　©　2021