The monomer–micelle equilibrium is shown to be responsible for an asymmetry between surfactant adsorption and desorption rates. When a solution containing micelles is brought into contact with a solid surface, the micelles dissociate to supply monomers that adsorb to the surface. When the same surface is subsequently exposed to a surfactant-free solution, desorption occurs slowly because of the higher affinity of the monomers to remain to the surface than to form micelles. As a result, the number of monomers that desorb is limited by the critical micelle concentration (CMC) of the surfactant. This effect is particularly pronounced for surfactants with low CMC values and in systems with high surface-to-volume ratios, such as porous media. A generic model is developed and applied to simulate the Ca2+-mediated adsorption and desorption of surfactants in limestone cores.