The adsorption and self-assembly of 1,3-phenylene diisocyanide (1,3-PDI) is studied on Au(111) using reflection-adsorption infrared spectroscopy (RAIRS), scanning tunneling microscopy (STM) and temperature-programmed desorption (TPD) supplemented by density functional theory (DFT) calculations and the results compared with the structures formed from 1,4-PDI where it assembled to form-(Au-PDI)oligomer chains that incorporate gold adatoms. The infrared spectra display a single isocyanide feature consistent with the isocyanide binding to gold adatoms while DFT calculations confirm that isocyanide binding to gold adatoms is more energetically favorable than binding to the surface. STM images show that 1,3-PDI forms zigzag chains containing hairpin bends that cause the chains to double back on each other, consistent with the 120º angle between the isocyanide groups. Hexagonal structural motifs are also observed that are proposed to be due to the self-assembly of three isocyanides as well as small structures that are assigned to 1,3-PDI dimers. The results suggest that the formation of gold-containing oligomers from isocyanide-containing molecules is a general phenomenon.