In order to understand the secondary recrystallization characteristics of high-permeability grain-oriented electrical steel, we studied microstructure, Goss orientation, onset secondary recrystallization temperature and Σ3, Σ5 and Σ9 grain boundaries during high temperature annealing. In particular, we examined the effect of different amounts of AlN inhibitors on the secondary recrystallization behavior. First, with the increase of AlN amount, the onset secondary recrystallization temperature and magnetic properties increase. Second, when the inhibitory ability is weak, the fraction of grains that have Goss±5, Goss±10, and Goss±15 keep constant before secondary recrystallization; with the increase of AlN amount, the fraction of grains that have Goss±15 keep almost constant, but the Goss±5 and Goss±10 grains increase obviously with the increase of temperature. Third, the frequency of Σ3, Σ5, Σ9 grain boundaries around Goss grains and general grains keeps almost constant with the increase of temperature before secondary recrystallization when having enough AlN inhibitors; however, when the content of AlN is very low, the frequency of Σ3, Σ5 and Σ9 grain boundaries around Goss grains will decrease to the level of that around general grains, which eventually leads to unsuccessful secondary recrystallization.