The adsorption structures of three thiophene derivatives and one pyrrole derivative on Au(1 1 1) have been investigated by scanning tunneling microscopy (STM) and cyclic voltammetry in 0.1 M HClO4. The structural details and differences of four monolayers are examined by STM. All the four monomers arrange into ordered adlayers at E = 0.55 V. Two kinds of alkyl substituted thiophenes, 3-hexylthiophene (HT) and 3-decylthiophene (DT), show similar adsorption behavior. Molecules form dimer basic units through S-S bonding and arrange into the "U-shaped like" patterns. 24(6-Bromohexyloxy)methyl)-2,3-dihydrothieno[3,4-b][1,4]dioxine (BDD) molecules with an 3,4-ethylenedioxythiophene (EDOT) as molecular skeleton assemble into liner structure with tetramers as building unit. 1-Octadecylpyrrole (ODP) with alkylated pyrrole ring form a lamella structure on Au(111) with interdigitated alkyl chains. The flat-lying configuration for the four monomers is beneficial to enhance the molecule-substrate interaction, which plays an important role to stabilize the organic thin film. (C) 2013 Elsevier BM. All rights reserved.