Amphiphilic poly(styrene-co-octadecyl maleamic acid salt) (PS-co-ODMAS) with a comb-like architecture was synthesized employing a heterophase aqueous polymerization reaction. The side-chain comonomer from octadecyl maleamic acid salt exhibited hydrogelation characteristics and provided conditions for a controlled polymerization reaction. PS-co-ODMAS polymers consisting of 5 and 10mol% side-chain monomer showed a high molecular weight on the order of 10 6 and narrow polydispersity index at 1.33+0.02. The polymer consisting of 10mol% side-chain monomer was shown to exhibit properties that are significantly different from those with 5mol%, and the control poly(styrene) synthesized using sodium dodecyl sulfate surfactant. The polymer consisting of 10mol% side-chain monomer formed hollow spherical spheres of 30nm size. It also showed close-packed structures of the side-chain monomer on the polymer surface. Detailed adsorption studies at the liquid/liquid interface were carried out to evaluate and understand the scope for modification in surface energy characteristics of polymers in the presence of additives drawn from simple surfactants. Triton X-100 was shown to undergo effective adsorption on the polymer consisting of 10mol% side-chain monomer and thus could generate stable emulsions with different volume fractions of heptadecane. The results from electron microscopy studies and viscosity of emulsions are discussed.