Investigating the effects of electrolyte ions on the adsorption configuration of methanol at a charged interface is important for studying the interface structure of electrolyte solutions and the oxidation mechanism of methanol in fuel cells. This study uses sum frequency generation (SFG) and heterodyne-detected second harmonic generation (HD-SHG) to investigate the adsorption configuration of methanol at the air/aqueous interface of 0.1 M NaClO4 solution, 0.1 M HClO4 solution and pure water. The results elucidate that the ion effect in the electrolyte solution affects the interface's charged state and the methanol's adsorption conformation at the interface. The negatively charged surface of the 0.1 M NaClO4 solution and the positively charged surface of the 0.1 M HClO4 solution arise from the corresponding specific ionic effects of the electrolyte solution. The orientation angle of methyl with respect to the surface normal is 43.4° ± 0.1° at the 0.1 M NaClO4 solution surface and 21.5° ± 0.2° at the 0.1 M HClO4 solution surface. Examining these adsorption configurations in detail, we find that at the negatively charged surface the inclined orientation angle (43.4°) of methanol favors the hydroxymethyl production by breaking the C-H bond, while at the positively charged surface the upright orientation angle (21.5°) of methanol promotes the methoxy formation by breaking the O-H bond. These findings not only illuminate the intricate ion effects on small organic molecules but also contribute to a molecular-level comprehension of the oxidation mechanism of methanol at electrode interfaces.