The interaction between cationic symmetrical gemini alkanediyl-alpha,omega-bis(dimethylcetylammonium bromide) series (16-s-16, s = 5, 6, abbreviated as G5 and G6) with hydrotropes (cationic: aniline hydrochloride, para-toluidine hydrochloride, and ortho-toluidine hydrochloride; nonionic: phenol, resorcinol, and pyrogallol) in aqueous medium has been investigated at four different temperatures ranging from 298.15 to 313.15 K. Different physico-chemical parameters such as critical micelle concentration (cmc), interaction parameter (beta(m), an energetic parameter that represents the excess Gibbs free energy of mixing), activity coefficients (f(i)), mole fraction of hydrotrope in mixed micelles at ideal mixing conditions (X(1)(ideal)), excess free energy of mixing (Delta(mix)G(E)), standard enthalpy (Delta(mic)H(o)), entropy (Delta(mic)S(o)), and Gibbs free energy (Delta(mic)G(o)) of micellization were evaluated and then intracompared. For further understanding, similar studies were carried out with their conventional counterpart cetyltrimethyl ammonium bromide (CTAB) and then compared. The bulk behaviors were explored using different theoretical models of Clint, Rubingh, and Motomura for justification and comparison of results of different binary combinations of hydrotropes with the gemini series and CTAB. Synergistic interaction was observed in all binary combinations at all temperatures in the micelles which decreases slightly with increasing temperature. This study will give insight into the selection of surfactants in different applications as their properties get modified by interaction with hydrotropes, thus influencing their solution behavior which, in turn, modifying the phase-forming behavior, microemulsion, liquid crystal forming systems, clouding phenomenon, cleaning, and laundry processes besides solubilization. The ability of hydrotropes to dramatically alter the solubility of other molecules in a medium can be exploited for the purpose of selective encapsulation and release.