The monolayer of ␣-sexithiophene on Ag͑001͒ has been studied by scanning tunneling microscopy and low-energy electron diffraction. Upon deposition at room temperature four well-ordered and commensurate molecular structures have been identified where the molecules adsorb flat lying with their long axis parallel to the ͓110͔ and ͓110͔ high-symmetry directions. Whereas three structures consist of straight molecules in alltrans configuration, one long-range ordered structure is observed where all molecules have undergone a trans-cis isomerization process between the second and third thiophene ring.
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