An SiO2–TiO2 closed-surface antireflective coating was fabricated by the one-dipping method. TiO2 nanoparticles were mixed with a nanocomposited silica sol, which was composed of acid-catalyzed nanosilica networks and silica hollow nanospheres (HNs). The microstructure of the sol–gel was characterized by transmission electron microscopy. The silica HNs were approximately 40–50 nm in diameter with a shell thickness of approximately 8–10 nm. The branched-chain structure resulting from acidic hydrolysis grew on these silica HNs, and TiO2 was distributed inside this network. The surface morphology of the coating was measured by field emission scanning electron microscopy and atomic force microscopy. After optimization, transmittance of up to 94.03% was obtained on photovoltaic (PV) glass with a single side coated by this antireflective coating, whose refractive index was around 1.30. The short-circuit current gain of PV module was around 2.14–2.32%, as shown by the current–voltage (IV) curve measurements and external quantum efficiency (EQE) tests. This thin film also exhibited high photocatalytic activity. Due to the lack of voids on its surface, the antireflective coating in this study possessed excellent long-term reliability and robustness in both high-moisture and high-temperature environments. Combined with its self-cleaning function, this antireflective coating has great potential to be implemented in windows and photovoltaic modules.