We report the synthesis of a new phenalenyl ligand, functionalized with a methyl ester electron withdrawing group, named 9-hydroxy-1-oxo-1H-phenalen-5-methyl carboxylate (L) and the generated complexes [Ru(bpy)2L]PF6 and [(η 6 -C6H6)Ru(L)Cl]. Compounds were characterized by spectroscopic and X-ray diffraction methods and their electrochemical behavior was investigated via cyclic voltammetry and UV-vis spectroelectrochemistry. The one-electron oxidized compounds have unpaired electron located in the phenalenyl ring, as supported by theoretical calculations (DFT) and EPR results. Langmuir-Blodgett (LB) films deposited by [Ru(bpy)2L] 2+/3+ species mixed with stearic acid are electroactive, showing quasi-reversible