The shear strength of unsaturated granite residual soil (GRS) will decline rapidly when moisture content increases, because of loss of matric suction in the soil. This can lead to slope instability and embankment collapse during rainfall. Determining the matric suction of GRS accurately at different conditions can improve the accuracy of stability analysis. Generally, matric suction can be characterized as the soil–water characteristic curve (SWCC), and it is closely related to soil microstructure. In this study, the entire range of matric suction was measured using a combination of pressure plate method, filter paper method, and vapor equilibrium method. Microstructure change was investigated based on mercury intrusion porosimeter tests, in which the pore size distribution (PSD) curves of GRS samples with different initial densities and moisture content were measured. The PSDs of samples before and after wetting were also measured and compared to investigate the influence of water intrusion. Test results indicate that the combination of measurement methods can cover the entire matric suction range. The microstructure of GRS with different initial conditions presents a clear bimodal PSD. At the same density, the increase in initial moisture content can increase intra-aggregate pores and decrease inter-aggregate pores. When initial density increases, only the volume of inter-aggregate pores decreases. Wetting can decrease inter-aggregate pores and increase intra-aggregate pores. Finally, the Li model is applied in SWCC fitting for tested samples, the result of which performs well with a high correlation coefficient (R2 > 0.95) and is recommended for GRS analysis.