Heterostructured　materials　integrate　the　advantages　of　adjustable　electronic　structure,　fast　electron/ions　transfer　kinetics,　and　robust　architectures,　which　have　attracted　considerable　interest　in　the　fields　of　rechargeable　batteries,　photo/electrocatalysis,　and　supercapacitors.　However,　the　construction　of　heterostructures　still　faces　some　severe　problems,　such　as　inferior　random　packing　of　components　and　serious　agglomeration.　Herein,　a　terminal　group-oriented　self-assembly　strategy　to　controllably　synthesize　a　homogeneous　layer-by-layer　SnSe2　and　MXene　heterostructure　(LBL-SnSe2@MXene)　is　designed.　Benefitting　from　the　abundant　polar　terminal　groups　on　the　MXene　surface,　Sn2+　is　induced　into　the　interlayer　of　MXene　with　large　interlayer　spacing,　which　is　selenized　in　situ　to　obtain　LBL-SnSe2@MXene.　In　the　heterostructure,　SnSe2　layers　and　MXene　layers　are　uniformly　intercalated　in　each　other,　superior　to　other　heterostructures　formed　by　random　stacking.　As　an　anode　for　lithium-ion　batteries,　the　LBL-SnSe2@MXene　is　revealed　to　possess　strong　lithium　adsorption　ability,　the　small　activation　energy　for　lithium　diffusion,　and　excellent　structure　stability,　thus　achieving　outstanding　electrochemical　performance,　especially　with　high　specific　capacities　(1311　and　839　mAh　g−1　for　initial　discharge　and　charge　respectively)　and　ultralong　cycling　stability　(410　mAh　g−1　at　5C　even　after　16000　cycles).　This　work　conveys　an　inspiration　for　the　controllable　design　and　construction　of　homogeneous　layered　heterostructures.　©　2023　Wiley-VCH　GmbH.