Li4Ti5O12　(LTO)　anode　is　a　promising　candidate　for　high-energy–density　lithium-ion　batteries　(LIBs),　but　achieving　high　mass　loading,　a　porous　structure,　and　efficient　ion　transport　remains　a　challenge.　Herein,　we　present　a　high-mass-loading,　hierarchically　porous　LTO　anode　with　a　conductive　network　and　grid-lined　micropores,　embedded　with　a　metal–organic　framework　(MOF)　as　both　an　electrode　additive　and　surface　protective　layer.　This　novel　structure　is　fabricated　using　extrusion-based　three-dimensional　(3D)　printing　technology.　The　self-standing　framework　provides　mechanical　stability　and　high　conductivity,　enabling　a　thick　(316　μm)　3D-printed　LTO@UiO-66-MOF　(3D-LTO@U)　anode　with　a　mass　loading　of　11　mg/cm2.　It　delivers　a　high-rate　capability　of　161　mAh/g　at　5C,　an　areal　specific　capacity　of　5.37　mAh/cm2,　and　78.9　%　areal　capacity　retention　after　150　cycles.　Additionally,　it　achieves　a　high　specific　energy　density　of　382.35　Wh/kg.　The　UiO-66　MOF　provides　strong　binding　affinity,　suppressing　side　reactions　and　enhancing　Li-ion/electron　transport　within　the　3D-printed　interconnected　channels.　This　improves　active　material　utilization　during　charge　and　discharge.　Furthermore,　a　3D-printed　full　cell　integrating　a　grid-lined　3D-LTO@U　anode　and　a　3D-printed　LiFePO4　cathode　exhibits　enhanced　electrochemical　performance.　This　work　demonstrates　an　effective　strategy　for　designing　thick,　high-mass-loading,　and　porous　conductive　network　anodes　for　advanced　LIBs.　©　2025　Elsevier　Inc.