An extrathin molecular superstructure can be constructed by combining planar molecules laid flat and arranged in a monolayer on a solid surface. We have introduced hydrogen bonds into a vapor-deposited monolayer on graphite to form a tapelike superstructure, atomic tape. A planar diamide suitable for linear connection 4,4′-[1,4-phenylenethynylene]-di(benzamide) (PDB) and a reference compound incapable of hydrogen bond formation4,4′-[1,4-phenylenethynylene]-bis(N,N-dimethylbenzamide) (PBDB) were designed and their monolayers were characterized by Penning ionization electron spectroscopy. It is found that the orientation of PDB molecules deposited at 130 K is random but changes to flat on heating to 195 K. Unlike the monolayers of PBDB and other larger compounds, the PDB monolayer does not sublime at 295 K. From these results it is considered that the atomic tape structure is formed by the intramonolayer hydrogen bonds of PDB. To elucidate the electronic structure of PDB and PBDB, the Penning ionization electron spectrum of gas phase PBDB was also measured and compared with the monolayer spectra.