Conventional surfactant dodecylbenzenesulfonic acid (DB SA) and its corresponding Gemini surfactant acid (GSA) were simply mixed with a solution of hyperbranched polyethylenimine (RPEI) in chloroform. This resulted in the novel supramolecular complexes, HPEI-DBSA and RPEI-GSA, through a neutralization reaction between the amino groups of RPEI and the sulfonic-acid groups of DBSA and GSA. The formed supramolecular complexes and their precursors were characterized by FTIR, $^1H$ NMR, and dynamic light scattering. HPEI-DBSA and HPEI-GSA exhibited inverted-micelle properties that could accommodate the water-soluble guest molecules in an apolar solvent. With the anionic dye methyl orange (MO) as the model guest, both RPEI-DBSA and HPEI-GSA showed superior guest-encapsulation performance than the supramolecular nanocarrier derived from the assembly of aliphatic acid onto HPEI. For example, HPEI-DBSA and RPEI-GSA nanocarriers could encapsulate more MO molecules, and a much smaller amount of the surfactant molecules was required to achieve the maximum MO encapsulation. These results highlight the importance of strong-acid groups of the surfactants in raising the guest-encapsulation efficiency of this type of supramolecular nanocarrier. HPEI-DBSA and HPEI-GSA had different guest-encapsulation mechanisms. This indicates that HPEI-GSA can encapsulate basic guests more than HPEI-DBSA, such as MO and fluorescein sodium (FS), but fewer relatively acidic guests, such as Alizarin Yellow R sodium salt and bromophenol blue.