Two new amphiphilic ionic liquids (AILs) were synthesized through the opening reaction of the epoxy ring of glycidyl 4-nonylphenyl ether (GNE) using ethanol amine (EA), followed by quaternization using bis(2-chloroethyl) ether (BCE) to form the corresponding IL (GEB-Cl). The chloride ion was replaced by a trifluoroacetate (TFA) ion to form the second IL (GEB-TFA). The chemical structures, surface tension, interfacial tension (IFT), and zeta-potential of the synthesized AILs were determined. Moreover, the efficiency of these AILs for breaking Arabian heavy crude oil emulsions was investigated. GEB-TFA showed high ability to reduce surface tension and IFT as well as high efficiency for demulsifying water/oil emulsions even at low concentrations of this IL.