Long-chain derivatives containing imidazole and benzimidazole moieties were newly synthesized and their monolayer behaviors and the complex formation with transition metal ions such as Ag(I),Cu(II),Fe(II) and Co(II) ions were investigated. Compared with the monolayer exhibiting plateau region on water surface, the long-chain derivative containing imidazole formed condensed monolayers by forming complexes with the above transition metal ions present in the subphase. The monolayers of benzimidazole derivatives formed stable complexes only with Ag(I) ion, which was confirmed by the isotherms of the monolayers and the ultraviolet measurements of the transferred Langmuir-Blodgett films. Different morphologies of monolayers of benzimidazole derivatives on water surface and the subphase containing Ag(I) ion were observed by Brewster angle microscopy.