In situ scanning tunneling microscope (STM) was used to examine the spatial structures of pentacene molecules adsorbed onto a Au(111) single-crystal electrode from a benzene dosing solution containing 16-400 μM pentacene. Molecular-resolution STM imaging conducted in 0.1 M HClO4 revealed highly ordered pentacene structures of (√31 × √31 )R8.9°, (3 × 10), (√31 × 10), and (√7× 2√)R19.1 ° adsorbed on the reconstructed Au(111 ) electrode dosed with different pentacene solutions. These pentacene structures and the reconstructed Au(111) substrate were stable between 0.2 and 0.8 V [vs reversible hydrogen electrode, RHE]. Increasing the potential to E > 0.8 V lifted the reconstructed Au(111) surface and disrupted the ordered pentacene adlattices simultaneously. Ordered pentacene structures could be restored by applying potentials negative enough to reinforce the reconstructed Au(111). At potentials negative of 0.2 V, the adsorption of protons became increasingly important to displace adsorbed pentacene admolecules. Although the reconstructed Au(111) structure was not essential to produce ordered pentacene adlayers, it seemed to help the adsorption of pentacene molecules in a long-range ordered pattern. At room temperature (25°C), ∼100 pentacene molecules seen in STM images could rotate and align themselves to a neighboring domain in 10 s, suggesting that pentacene admolecules could be mobile on Au(111 ) under the STM imaging conditions of -150 mV in bias voltage and 1 nA in feedback current.