Blood oxygenation level-dependent (BOLD) contrast appears through a variation in the transverse relaxation rate of magnetic resonance signals induced by neurovascular coupling and is known to have nonlinear characteristics along echo time (TE) due to the intra-vasculature. However, the physiological causes of this nonlinearity are unclear. We attempted to estimate the physiological information related to the nonlinearity of BOLD signals by using a two-compartment model. For this purpose, we used a multi-echo gradient-echo echo-planar imaging sequence and developed a computational method to estimate the physiological information from the TE-dependent BOLD signals. The results showed that the average chemical exchange time in the intra-vasculature varied during stimulation, which might be the essential source of the nonlinearity.