Fine structures in ceramics are important for enhancing the electrical, thermal, optical and mechanical properties of ceramics. Magnetic field alignment of the crystal orientations of fine particles is one of the most effective methods for controlling fine structures. We used neutron diffraction to investigate magnetic alignment of α-Al2O3 fine particles. In situ neutron diffraction measurements of the suspension were performed to investigate the effect of applying a magnetic field. The results revealed that the balance between the magnetic anisotropy energy and thermal fluctuations is critical in determining the crystal orientations of the α-Al2O3 particles in the suspension. Samples were produced by systematically varying the sintering temperature. They were used for neutron diffraction measurements to investigate the effect of sintering. We found that the crystal orientation improves dramatically at temperatures above the grain growth temperature. In this review, we present the experimental details of the neutron diffraction measurements and analyze the results.