Solvent effect on the formation and electrochemical behavior of octaneselenolate (C8Se) self-assembled monolayers (SAMs) on Au(111) derived from the adsorption of octaneselenocyanate (C8Se-CN) molecules in various solvents at 363 K for 1 h was examined by scanning tunneling microscopy (STM) and cyclic voltammetry (CV). STM imaging clearly revealed that the formation and structure of C8Se SAMs were markedly influenced by the polarity of solvent. C8Se SAMs formed in octane were composed of liquid-like disordered phase. In contrast, C8Se SAMs formed in DMF had ordered domains but not a uniform surface, whereas C8Se SAMs formed in ethanol had uniform surface and highly ordered domains with a (2 × 2 √13) structure. It was found that the structural quality of C8Se SAMs increased with increasing solvent polarity in the order of ethanol > DMF > octane. CV measurements also showed that blocking efficiency of C8Se SAMs for electrode reaction increased with increasing the structural quality of SAMs.