This paper presents a facile method to synthesize monodisperse SrTiO3 hollow spheres with one or two openings through a template-assisted approach. These hollow spheres were further self-assembled into densely packed nanofilms at a "hexane-water" interface. TEM, SEM, HRTEM, XRD, etc., were employed to characterize the morphology and structure of the SrTiO3 hollow spheres as well as the corresponding nanofilms. The nanofilm-based photodevice displayed considerably higher sensitivity to UV than visible light and dark.