Recent work has focused on removing mercury from contaminated water via microemulsion liquid membranes. Electrostatic coalescence and butanol addition are evaluated as potential demulsification techniques for recovery of the components of mercury-rich microemulsions. Unlike coarse emulsions, electrical demulsification with heat is not effective for microemulsions due to the smaller size of the internal phase droplets in microemulsions. This explanation is confirmed by the photomicrographs of the two emulsion systems. Microemulsions can be demulsified using butanol as an additive. The demulsification kinetics are proportional to the butanol concentration and the temperature and inversely proportional to the surfactant concentration. Reduced mercury extraction efficiency with microemulsions formulated from recovered oil phase is attributed to some surfactant degradation during the demulsification processing as well as residual butanol in the recycled organic phase.