Chemically stabilized emulsions are difficult to break because of micelle stability. Many physical and chemical processes have been used for emulsion breaking/separation; however, most operational parameters are based on empirical data and bulk analysis. A multiscale understanding of emulsions is required before these processes can advance further. This study utilized needle-type microsensors and confocal laser scanning microscopy (CLSM) for characterizing simulated bilge water emulsions with different types of surfactants (Triton X-100 and sodium dodecyl sulfate [SDS]) under various NaCl concentrations at microscale. Using microsensors, a diffusion process was clearly visualized across the oil/water interface which appears to be related to emulsion formation kinetics and mass transfer. While emulsion stability decreased with NaCl concentrations, SDS (anionic surfactant) is more likely to form emulsion as salinity increases, requiring more salinity to coalesce SDS emulsions than Triton X-100 (nonionic surfactant) emulsions. Triton X-100 emulsions showed the potential to exhibit particle stabilized emulsions with NaCl concentration below 10(-2.5) M. The research demonstrated that the use of nonionic surfactant allows better oil-in-water separation than anionic surfactant. Significant pH changes of emulsions from unknown additives have implications when operating pH-sensitive emulsion breaking/separation processes (e.g., electrocoagulation).