Langmuir and Langmuir–Blodgett films have been fabricated from an acetylene-terminated phenylene–ethynylene oligomer, namely 4-((4-((4-ethynylphenyl)ethynyl)phenyl)ethynyl)benzoic acid (HOPEA). Characterization of the Langmuir film by surface pressure vs area per molecule isotherms and Brewster angle microscopy reveals the formation of a high quality monolayer at the air–water interface. One layer Langmuir–Blodgett (LB) films were readily fabricated by the transfer of HOPEA Langmuir films onto solid substrates by the withdrawal of the substrate. The deposition mode was Z-type. Quartz crystal microbalance (QCM) experiments confirm the formation of directionally oriented, monolayer LB films, in which the HOPEA molecules are linked to the gold substrate by attachment through the acid group. The morphology of these films was analyzed by atomic force microscopy (AFM), which revealed an optimum transference surface pressure of 18 mN m–1 for the formation of homogeneous films. Cyclic voltammetry also showed a significant blockage of gold electrodes covered by HOPEA monolayers. Electrical properties of HOPEA monolayers sandwiched between a bottom gold electrode and a gold STM (scanning tunneling microscope) tip have been recorded, revealing that the acetylene group is an efficient linker for electron transport. In addition, the STM experiments indicate a nonresonant tunneling mechanism of charge transport through these metal–molecule–metal junctions.