A -conjugated compound with two thioacetate end groups was synthesized using a recently developed method. A selfassembled monolayer (SAM) of corresponding dithiol was prepared by dipping a Au(111) surface for 1 min in a 2 mM dithiol toluene solution formed 30 min after the addition of a drop of 30% NH 4 OH in water to the dithioacetate toluene solution. We investigated electronic conduction through isolated single molecules of the -conjugated compound by statistical analysis of molecular junctions repeatedly formed between a gold tip and the SAM on Au(111) using scanning tunneling microscopy (STM) under ultrahigh vacuum (UHV). The single-molecular conductivity of the -conjugated compound is described as G m ¼ T contact with tip Á T -system Á T contact with substrate Á G 0 according to the Landauer equation. Here, Ts are transmission functions and G 0 is the quantum conductance, i.e., 2e 2 =h. Because of observed high values of G m for the -conjugated compound, we could readily analyze the effect of molecule-electrode contacts on T contact with tip Á T contact with substrate . Namely, we successfully observed the dependence of T contact with tip Á T contact with substrate on binding sites of -S À on a Au(111) surface, i.e., the bridge (or the hollow) and the top sites.