3-Aminopropyl-trimethoxysilane was introduced into bis-triazinyl amino-stilbene through the condensation reaction to obtain fluorescent whitening agents (FWAs) having excellent photo-stability. Tetraethoxysilane was hydrolyzed and combined with FWAs through in situ polymerization to obtain nanosilica-loaded yellowing inhibitors (SiO2–FWAs). Ultraviolet (UV) spectroscopy showed that the ratios of the trans-isomer structure in FWAs after 3 h of UV irradiation was 5.41 times higher than those of the cis-isomer. Moreover, the absorption intensity in the UV region was increased distinctly after nano-silica loading. Fluorescence spectroscopy revealed that the fluorescence of SiO2–FWAs was more intense than that of FWAs. In addition, the fluorescence quantum yield of SiO2–FWAs reached 0.416, whereas that of the default FWAs was only 0.279. UV-aging test results showed that SiO2–FWAs can improve the initial whiteness and anti-yellowing performance of paper made from high-yield pulp (HYP). These results indicated that the as-prepared SiO2–FWAs not only exhibited more excellent UV absorption and fluorescence emission properties, but it also exerted better whitening and anti-yellowing effects on high-yield pulp paper than the default FWAs. The enhanced performance of SiO2–FWAs can be ascribed to the synergy between the excellent UV-scattering effect of nanosilica and the fluorescent whitening property of FWAs.