A series of amphiphilic oligomers have been synthesized in which the hydrophobic component was polyisobutylene, polystyrene, poly(methyl methacrylate) or dodecane, and the hydrophilic component was poly(vinyl alcohol) or poly(methacrylic acid). These syntheses exploited the chain extension chemistry of aldehyde-functionalized materials using silyl aldol polymerization or the group transfer polymerization of methacrylates. The interfacial character of these new amphiphilic oligomers was examined using water/toluene emulsification tests.