Although　in-plane　heterostructure　with　high　ion　transport　pathway　and　unique　interfacial　atomic　structure　offers　endless　possibilities　in　the　catalysis　field,　it　is　still　challenging　to　directly　synthesize　MXene-based　in-plane　heterostructure　due　to　the　differences　in　crystal　structures　and　growth　conditions.　Here,　Mo2C–MoS2　in-plane　multi-heterostructures　are　synthesized　by　topological　conversion　of　sandwich-like　mesoporous　Mo2C–SiO2　layers　in　sulfur　vapor　and　subsequent　removal　of　SiO2.　During　the　conversion　process,　the　exposed　Mo2C　will　efficiently　converted　to　2H　phase　MoS2,　meanwhile,　the　covered　Mo2C　remained　stable,　affording　metallic　Mo2C　MXene　and　semiconducting　MoS2　in-plane　multi-heterostructures　compatible　in　one　layer.　The　resultant　Mo2C–MoS2　layer　has　multiple　heterointerfaces,　build-in　electric　fields　as　well　as　abundant　defects.　Such　structural　features　enable　to　improve　of　the　electrochemical　active　surface　area　(16.4 mF cm−2),　which　not　only　facilitates　the　bidirectional　sulfur　electrochemistry　between　solid　Li2S　and　soluble　lithium　polysulfides,　but　also　enhances　the　transfer　kinetics　of　electrons　and　ions,　giving　rise　to　a　high-rate　performance　(642 mAh g−1　at　5 C)　and　a　long-term　cycle　life　(1000　cycles　at　5 C)　in　lithium–sulfur　batteries.　©　2024　Wiley-VCH　GmbH.