The photoassisted fusion of a decanethiol-passivated Au-nanoparticle film on a glass substrate by exposure to vacuum-ultraviolet (vacuum-UV) light at 172 nm was investigated and compared to that by thermal fusion. On the basis of the thermal treatment at 200 degrees C, the X-ray diffraction patterns indicated that the Au-nanoparticle film with the particle diameter of 2.1 nm is completely converted to a crystalline Au film, and the film surface was coarsely granular, having a roughness of several tens of nanometers by field emission-scanning electron microscopy observation. After exposure to vacuum-UV light, the UV-vis absorption spectra revealed that the surface plasmon band at 535 nm showed a red shift with the increasing exposure time, and then the absorption band at 770 nm was clearly observed at 30 min. The diameter of the fused Au nanoparticles was larger than 20 nm on the basis of a transmission electron microscopy observation. These changes indicated that the Au nanoparticles were converted to the crystalline state due to photodecomposition of the decanethiol. Thus, the controllable mild fusion among neighboring Au nanoparticles at room temperature was achieved by vacuum-UV-light exposure due to photodecomposition of the decanethiol.