We investigated the molecular arrangement and surface morphology of organized molecular films of the 3-arm comb polymer containing metal ion us surface pressure-area (π-A) isotherm, inductively-coupled plasma mass spectrometry (ICP-MS), in-plane and out-of plane X-ray diffraction (XRD), and atomic force microscopy (AFM). From the result of WAXD measurement of the corresponding monomer in bulk, the long hydrocarbon chains are packed hexagonally in solid-state. Compared with their monolayer on the distilled water as subphase, that of this compound on buffer solution containing Cd²⁺ ion is remarkably expanded at 15°C. It is found that highly ordered layer structures and two-dimensional lattices are constructed in the organized molecular films of Cd-bridged comb polymer using in-plane and out-of plane XRD. Further, surface morphology of the LB films fabricated from the monolayers on buffer solution including Cd²⁺ formed flat and smooth domains by metal-scavenging.