Through penetration depth tests, capillary water absorption tests under different abrasion depths, and capillary water absorption tests of a cement mortar test block with crack damage, a self-prepared, novel, graphene oxide/silane composite emulsion used for the effect of wear or cracking damage was studied. The waterproof performance of concrete and the protective mechanism of a composite emulsion was verified by scanning electron microscopy, X-ray diffraction, and thermogravimetric analysis. The test results showed that the penetration depth of the composite emulsion reached depths greater than 9 mm, which yielded a good waterproof effect; when the concrete was cracked or worn, the composite emulsion still had a stable waterproof performance. It was found that the composite emulsion could form a hydrophobic layer with a certain thickness inside the cement-based material, which explains why the composite emulsion had a good waterproof effect.