Bolaamphiphilic-type structures can be effective substitutes to conventional surfactants for the interaction and stabilization of colloidal interfaces in water. Different families of bolaamphiphiles were used as a growth control and stabilizing agent for the formation of gold nanoparticles (AuNPs). The nature of polar heads and the length of hydrophobic chain are key parameters for modulating the interaction with gold surfaces. In particular, interactions between hydrophobic chains dramatically strengthen the interactions with NP surfaces leading to a reversible aggregation process. This affects not only the gold nanoparticle growth mechanism and stabilization properties but also the catalytic properties of the modified gold nanoparticles.