The grain-oriented silicon steel is a kind of important magnetic materials with low iron loss and high induction. Hot band normalizing annealing is an important process which influences the microstructure and the development of the inhibitors. The effects of different annealing temperatures and cooling conditions on the inhibitors and microstructures of normalizing annealing band were investigated. The microstructure and different kinds of the inhibitors, i.e., AlN, AlN+CuxS+MnS, and TiN, were discovered. The result shows that a suitable cooling condition leads to more nano-scale inhibitors and uniform microstructure of the normalizing annealing band and consequently results in better magnetic properties.