Present communication reports the preparation of Langmuir monolayer of water-soluble anionic dye Congo red (CR) by allowing it to adsorb from the aqueous subphase onto the preformed Langmuir monolayer of anionic stearic acid using divalent metal cations Mg2+ as mediator. Isotherm and compressibility studies of SA-Mg-CR hybrid monolayer gave valuable information about the molecular organisation in the Langmuir monolayer. Absorption spectroscopic studies revealed the formation of H-aggregates in the hybrid Langmuir–Blodgett (LB) films fabricated at lower salt concentration in the subphase. Atomic Force Microscopic image gave visual evidence of distinct nanocrystalline domains in the LB monolayer film.