In the current study, we used micromodel experiments to study three-phase fluid flow in porous media. In contrast to previous studies, we simultaneously observed and measured pore-scale fluid behavior and three-phase constitutive relationships with digital image acquisition/analysis, fluid pressure control, and permeability assays. Our results showed that the fluid layers significantly influenced pore-scale, three-phase fluid displacement as well as water relative permeability. At low water saturation, water relative permeability not only depended on water saturation but also on the distributions of air and diesel. The results also indicate that the relative permeability–saturation model proposed by Parker et al. (1987) could not completely describe the experimental data from our three-phase flow experiments because these models ignore the effects of phase distribution. A simple bundle-of-tubes model shows that the water relative permeability was proportional to the number of apparently continuous water paths before the critical stage in which no apparently continuous water flow path could be found. Our findings constitute additional information about the essential constitutive relationships involved in both the understanding and the modeling of three-phase flows in porous media.