SiO2, an insulator, hardly has any photocatalytic acitivity due to its intrinsic property, and it is generally used as a hard template to increase the surface area of catalysts. However, in this work, we found that the surface state of the insulator SiO2 can promote the migration of photogenerated charge carriers, leading to the enhancement of the photooxidation ability of graphitic carbon nitride (g-C3N4). A one-pot calcination method was employed to prepare g-C3N4/SiO2 composites using melamine and SiO2 as precursors. The composites present considerably high photocatalytic degradation activities for 2,4-dichlorophenol (2,4-DCP) and rhodamine B (RhB) under visible light (λ > 420 nm) irradiation, which are about 1.53 and 4.18 times as high as those of bulk g-C3N4, respectively. The enhancement of the photocatalytic activity is due to the fact that the introduction of the insulator SiO2 in g-C3N4/SiO2 composites can greatly improve the specific surface area of the composites; more importantly, the impurity energy level of SiO2 can help accelerate the separation and transfer of electron-hole pairs of g-C3N4. Electron paramagnetic resonance (EPR) spectroscopy and trapping experiments with different radical scavengers show that the main active species of g-C3N4 are superoxide radicals, while holes also play a role in photodegradation. For g-C3N4/SiO2-5, besides superoxide radicals and holes, the effect of hydroxyl radicals was greatly improved. Finally, a possible mechanism for the photogenerated charge carrier migration of the g-C3N4/SiO2 photocatalyst was proposed.