Novel surface active maleate and methacrylate monomers based on derivatives of ω‐hydroxy carboxylic acids have been synthesized. The monomers are comprised of hydrophobic alkyl chains and hydrophilic poly(ethylene glycol), quaternary ammonium, sulfonate and carboxylic fragments. Synthesized monomers sufficiently reduce surface tension at the aqueous solution‐air interface. The copolymerization of synthesized monomers with 5‐tert‐butylperoxy‐5‐methyl‐2‐hexene‐3‐yne monomer and N‐vinylpyrrolidone in solvent and emulsion copolymerization of synthesized peroxide containing surface active monomer with styrene have been carried out. The synthesized surface active monomers have been shown to be suitable emulsifiers for obtaining polystyrene colloid dispersions. It has been ascertained that the surface active copolymers obtained can form stable interpolyelectrolyte complexes with oppositely charged polymers.