Disclosed and claimed is a microemulsion-based demulsifier composition and a method of demulsifying an emulsion comprising hydrocarbon and water. The demulsifier composition includes (i) an oil-like phase comprising at least one nonionic surfactant having a hydrophilic-lipophilic balance (HLB) of less than about 9; (ii) a coupling agent capable of stabilizing the demulsifier composition; (iii) at least one water-soluble or dispersible nonionic surfactant that is different from the at least one nonionic surfactant in the oil-like phase; (iv) at least one additional surfactant selected from anionic, cationic, amphoteric, and combinations thereof; (v) at least one nonionic demulsifier; and (vi) water.