The micellar and surface properties of single as well as equimolar binary mixed systems of some cationic gemini and monomeric ionic surfactants have been studied by conductivity, surface tension and fluorescence measurements at 300K. The critical micelle concentration (CMC), Γmax (maximum surface excess), Amin (minimum surface area per molecule), πcmc (surface pressure at the CMC) and thermodynamic parameters viz. standard Gibbs free energies of adsorption (ΔGads°), standard Gibbs free energies of micellization (ΔGm°) and minimum free energy of the surface (ΔGmin(s)) of gemini with cationic monomeric surfactants were also evaluated. The negative values of ΔGads° and ΔGm° indicate the spontaneity and stability of the mixed micelle. The experimental CMC values are less than the ideal CMC values, indicating negative deviation from ideal behavior for all the equimolar binary surfactant systems. Aggregation number (Nagg) and Stern–Volmer quenching constant (Ksv) have been evaluated by Fluorescence measurement. The solubilization capacities of selected single and equimolar binary surfactant systems toward polycyclic aromatic hydrocarbons (PAHs), i.e., naphthalene, anthracene and pyrene have been evaluated and discussed in terms of the molar solubilization ratio (MSR), the micelle-water partition coefficient (K(m)), the deviation ratio (R), and the free energy of solubilization (ΔGs°) of PAHs. The negative value of ΔGs° shows spontaneity of solubilization process.