The use of pH dependent cleavable single ester bonded twin tailed gemini surfactant, 2, 2’-[(oxybis (ethane-1,2-diyl))bis (oxy)]bis (N-hexadecyl-N,Ndimethyl-2-oxoethanaminium) dichloride (C16–C4O2–C16), for the Surfactant Enhanced Remediation (SER) of various PAHs having different hydrophobicities is reported for the first time. The solubilization capabilities of aqueous micellar solutions of C16–C4O2–C16 were investigated at pH 3, 7 and 12. To understand the effect of pH-dependent aggregation on solubilization efficiency of the said surfactant, the solubilization parameters were quantified in terms of Micellar Solubilization Ratio (MSR) and micelle-water partition coefficient (K_m). The locus of solubilization of PAHs and their mutual interactions were studied by ¹H-NMR at different pH values. It was concluded from the MSR values of naphthalene (Np), phenanthrene (Ph), pyrene (Py), perylene (Pe) that single solute solubilization efficiency increases with the increase in pH of the surfactant media owing to increase in the size of micellar scaffolds and aggregation number. While in binary and ternary mixtures there was either synergism as in Ph-Py at pH 7 or antagonism as in Ph–Py at pH 3, depending upon the solute–solute and solute-solubilizate interactions. This study provides valuable insights into the potential applications of Gemini surfactant for the cosolubilization of hydrophobic compounds at different pH values.