Structural　modulation　endows　electrochemical　hybrids　with　promising　energy　storage　properties　owing　to　their　adjustable　interfacial　and/or　electronic　characteristics.　For　MXene-based　materials,　however,　the　facile　but　effective　strategies　for　tuning　their　structural　properties　at　nanoscale　are　still　lacking.　Herein,　3D　crumpled　S-functionalized　Ti3C2Tx　substrate　is　rationally　integrated　with　Fe3O4/FeS　heterostructures　via　coprecipitation　and　subsequent　partial　sulfurization　to　induce　a　highly　active　and　stable　electrode　architecture.　The　unique　heterostructures　with　tuned　electronic　properties　can　induce　improved　kinetics　and　structural　stability.　The　surface　engineering　by　S　terminations　on　the　MXene　further　unlocks　extra　(pseudo)capacitive　lithium　storage.　Serving　as　anode　for　lithium　storage,　the　optimized　electrode　delivers　an　excellent　long-term　cycling　stability　(913.9　mAh　g(-1)　after　1000　cycles　at　1　A　g(-1))　and　superior　rate　capability　(490.4　mAh　g(-1)　at　10　A　g(-1)).　Moreover,　the　(de)lithiation　pathways　associated　with　energy　storage　mechanisms　are　further　revealed　by　operando　X-ray　diffraction,　in　situ　electroanalytical　techniques,　and　first-principles　calculations.　The　hybrid　electrode　is　proved　to　undergo　stepwise　phase　transformations　during　discharging　but　a　relatively　uniform　reconversion　during　charging,　suggesting　an　asymmetric　conversion　mechanism.　This　work　provides　a　novel　strategy　for　designing　high-performance　hybrids　and　paves　the　way　for　in-depth　understanding　of　complex　lithium　intercalation　and　conversion　reactions.