Scanning tunneling microscopy has been used to obtain images of the surface conformations of 4‐n‐octyl‐4’‐cyano‐biphenyl, a room‐temperature smectic liquid crystal. Working in air and using the constant‐current mode, it has been possible to resolve both the aliphatic and aromatic parts of the molecule, and to observe individual benzene rings. Two previously unreported structures have been observed: an overlapping bilayer of layer spacing 37 Å, and a densely packed monolayer of spacing 24 Å. Periodic dislocations in the molecular packing have also been observed. Surface forces and intermolecular interactions are discussed as factors which could lead to these observed structures.