Due to the formational environment and climatic variability, granite residual soils with grain-size distribution ranging from gravel to clay undergo multiple drying–wetting cycles. The influences of multiple drying–wetting cycles on the soil-water characteristic curve (SWCC) and pore-size distribution (POSD) of undisturbed granite residual soils are investigated using the pressure plate test and nuclear magnetic resonance (NMR) spin-spin relaxation time (T2) distribution measurement, respectively. Results show that the water-retention capacity and air-entry value decrease and pores become more uniform with increasing drying–wetting cycles. After four drying–wetting cycles, the soil reaches a nearly constant state. The POSD change of multiple drying–wetting cycle samples is consistent with the SWCC of the soils. Furthermore, a modified van Genuchten model in terms of cumulative pore volume is used to obtain the best-fit POSD of the drying–wetting cycle samples. The shape and changing tendency of both curves of SWCC and POSD are quite similar and achieved a better correlation. It can be concluded that the SWCC is strongly dependent on the POSD of the soil and NMR T2 relaxometry can be used as an alternative to the assessment of microstructural variation of residual soils subjected to the periodic drying and wetting process.