A series of pyridine- and phenol-based ruthenium(II)-containing amphiphiles with bidentate ligands of the following types are reported: [(L-PyI)Ru-II(bPy)(2)](PF6)(2) (1), [(L-PyA)Ru-II(bpy)(2)](PF6)(2) (2), [(L-PhBuI)Ru-II(bpy)(2)](PF6) (3), and [(L-PhCII)Ru-II(bpy)(2)](PF6) (4). Species 1 and 2 are obtained by treatment of [Ru(bpy)(2)Cl-2] with the ligands L-PyI (N-(pyridine-2-ylmethylene)octadecan -1-amine) and L-PyA (N-(pyridine-2-ylmethyl)octadecan-1-amine). The imine species 3 and 4 are synthesized by reaction of [Ru(bpy)(2)(CF3SO3)(2)] with the amine ligands HLPhBuA (2,4-di-tert-butyl-6-((octadecylamino)methyl)phenol), and HLPhCIA (2,4-dichloro-6-((octadecylamino)methyl)phenol). Compounds 1-4 are characterized by means of electrospray ionization (ESI+) mass spectrometry, elemental analyses, as well as electrochemical methods, infrared and UV-visible absorption and emission spectroscopies. The cyclic voltammograms (CVs) of 1-2 are marked by two successive processes around -1.78 and -2.27 V versus Fc(+)/Fc attributed to bipyridine reduction. A further ligand-centered reductive process is seen for 1. The Ru-II/Ru-III couple appears at 0.93 V versus Fc(+)/Fc. The phenolato-containing 3 and 4 species present relatively lower reduction potentials and more reversible redox behavior, along with Ru-II/III and phenolate/phenoxyl oxidations. The interpretation of observed redox behavior is supported by density functional theory (DFT) calculations. Complexes 1-4 are surface-active as characterized by compression isotherms and Brewster angle microscopy. Species 1 and 2 show collapse pressures of about 29-32 mN.m(-1), and are strong candidates for the formation of redox-responsive monolayer films.