Microemulsions are transparent, thermodynamically stable liquid mixtures of oil, water and surfactant. They typically exist in the form of micellar and bicontinuous structures, which appear to be equilibrium systems but are actually complex in structure and are difficult to characterize at the molecular level. In this work, potassium ferrocyanide [K₄Fe(CN)₆] and tungsten hexacarbonyl [W(CO)₆] were chosen as two probe molecules for water and organic phases respectively to simultaneously explore the structures and dynamics of commonly prepared reverse micellar and bicontinuous microemulsion structures using aerosol OT (AOT) as the surfactant and isooctane as the oil phase. Even though these two structures have quite different solvent environments due to the varying geometry and boundary conditions, the steady-state infrared spectra of the CN⁻ stretching mode in the water phase are quite similar, and so are those of the CO stretching mode in the oil phase. However, vibrational and anisotropic relaxation dynamics obtained from infrared pump–probe spectroscopy and spectral diffusion dynamics extracted from two-dimensional infrared spectroscopy of the two infrared chromophores in the two probe molecules are found to be quite sensitive to whether the probe molecules are in pure solvent or in a restricted microemulsion environment. The results in the water phase and oil phase are discussed separately. Our work demonstrated that ultrafast nonlinear infrared spectroscopy can be used to differentiate the structural details at the molecular level for different microemulsion systems.