Self-assembling systems based on amphiphilic alkyltriphenylphosphonium bromides: Elucidation of the role of head group

► Micellization of surfactants with phosphonium and ammonium head group is compared. ► Solubilization and micellization capacity monotonously change with alkyl chain length. ► Surface tension isotherms and counterion binding differ for low and high homologues. ► Krafft temperatures for phosphonium series are lower compared to ammonium series. ► Solubilization capacity of phosphonium series is higher compared to that of ammonium series.