Aurophilicity is a well-known phenomenon in structural gold chemistry and found in many crystals of Au(I) complexes. However, these attractive dispersion forces between and within complexes containing Au(I) moieties are not well studied in ultrathin films. In this article, we elucidate the interaction of chlorido(2-naphthyl isonitrile)gold(I) ((NapNC)Au(I)Cl) on and with Au(110) and Au(111) surfaces. Already during physical vapor deposition, the condensation of ultrathin films is monitored by photoelectron emission microscopy (PEEM) and by incremental and spectrally resolved changes in optical reflectance (DDRS). Additional structural data obtained by STM and LEED reveal that the `crossed swords' packing motif known from the bulk is also present in thin films.