An organic-inorganic hybrid coating with spatial structures is known to be potential for biology, catalysis, and electrochemistry, but no report of basket-weave structure made from organic component has been available. Here, we report a molecular self-assembly to create the basket-weave organic structure using dimethyl-5-hydroxyisophthalate ( DMIP). Primary clusters of DMIP precipitated on the porous surface of inorganic layer by the use of beneficial effect of the micro-defects which triggers the physical locking activated by charge-transfer phenomena. Then, the organic chain grows on a certain plane, resulting from the non-covalent pi-pi stackings between short-range ordered aromatic cores as well as the interactions between polar functional groups. A detailed analysis on surface morphologies suggests that two adjacent basket-weaves are linked together through kinds of non-covalent interactions between functional groups of each weave. Thus, the molecule agglomerates of basket-weave organic component formed on defective inorganic layer are the primary source for extraordinary electrochemical stability.