Improving the efficiency of electric vehicle traction motors requires non-oriented silicon steels with low core loss and favorable magnetic induction. This study aims to clarify the influence of annealing temperature on the microstructure, texture, and magnetic properties of a 3.2%Si–0.9%Al steel, providing guidance for process optimization. Optical metallography, X-ray diffraction, and electron backscatter diffraction were employed to characterize the evolution. Recrystallization was completed between 620 °C and 720 °C, during which fine recrystallized grains replaced the deformed structure, accompanied by the nucleation of {111} and {114} grains. With further annealing from 850 °C to 1050 °C, grain growth occurred, resulting in an α*-fiber texture dominated by {114}. The fraction of high-angle {114} grains increased, while low-angle {111} grains decreased. This microstructural evolution significantly influenced the magnetic properties of non-oriented electrical steel. The P_1.5/50 and P_1.0/400 core losses reached minimum values of 2.02 W/kg and 16.48 W/kg at 1010 °C and 930 °C, respectively, while B₅₀ decreased slightly from 1.670 T to 1.652 T. These findings indicate that precise control of the annealing temperature is an effective strategy to tailor microstructure and texture, thereby optimizing the magnetic properties of non-oriented electrical steel.