Van der Waals(vdW)integration affords semiconductor heterostructures without constrains of lattice matching and opens up a new realm of functional devices by design.A particularly interesting approach is the electrochemical intercalation of two-dimensional(2D)atomic crystal and formation of superlattices,which can provide scalable production of novel vdW heterostructures.However,this approach has been limited to the use of organic cations with non-functional aliphatic chains,therefore failed to take the advantage of the vast potentials in molecular functionalities(electronic,photonic,magnetic,etc.).Here we report the integration of 2D crystal(MoS2,WS2,highly oriented pyrolytic graphite(HOPG),WSe2 as model systems)with electrochemically inert organic molecules that possess semiconducting characteristics(including perylene-3,4,9,10-tetracarboxylic dianhydride(PTCDA),pentacene and fullerene),through on-chip electrochemical intercalation.An unprecedented long-range spatial feature of intercalation has been achieved,which allowed facile assembly of a vertical MoS2-PTCDA-Si junction.The intercalated heterostructure shows significant modulation of the lateral transport,and leads to a molecular tunneling characteristic at the vertical direction.The general intercalation of charge neutral and functional molecules defines a versatile platform of inorganic/organic hybrid vdW heterostructures with significantly extended molecular functional building blocks,holding great promise in future design of nano/quantum devices.