Water diffusivity, a critical parameter for cereal processing design and quality optimization, is usually concentration-dependent. dynamic vapor sorption (DVS) system provides an approach to establishing the relationship between water concentration and diffusivity. However, the usual relative humidity (RH) jump during practical sorption processes is usually greater than that adopted in DVS measurements. Water vapor sorption kinetics of glutinous rice grains, glutinous rice flour and wheat flour dough films were measured using the DVS system to verify if varying RH step sizes can obtain identical diffusivities within the same range. The effective diffusivities were determined according to Fick’s second law. The results revealed that increasing RH step size led to a higher estimated diffusivity, regardless of whether the water concentration gradient or potential chemical gradient was considered a driving force for water diffusion. This finding was further confirmed by a linear RH scanning DVS measurement. The water concentration-dependent diffusivity obtained from a multi-step DVS measurement, according to Fick’s second law, will overestimate the required time for practical cereal drying or adsorption. Thus, this paradoxical discrepancy needs a new mass transfer mechanism to be explained.