The composition and structural parameters of W/O microemulsions containing the gemini surfactant 1,4-bis(3-alkylimidazolium-1-yl) butane bromide [(C n -4-C n )Br 2 , n = 12, 14, 16] + pentan-1-ol + octane + water and W/O microemulsions containing the ionic liquid surfactant 1-alkyl-3-methylimidazolium (C n mimBr, n = 12, 14, 16) + pentan-1-ol + octane + water were studied and compared. The mole fractions of the n -alkyl alcohol at the interfacial layer $$X_{\text{a}}^{\text{i}}$$ X a i in (C n -4-C n )Br 2 based microemulsion systems are always larger than those in C n mimBr based microemulsion systems. However, the mole fractions of the n -alkyl alcohol in the oil phase $$X_{\text{a}}^{\text{o}}$$ X a o are nearly the same for both the microemulsion systems. The (C n -4-C n )Br 2 based microemulsion systems have greater absolute values of the free enthalpy values $$- \Delta G_{{{\text{o}} \to {\text{i}}}}^{\text{o}}$$ - Δ G o → i o than that for C n mimBr based systems. In the (C n -4-C n )Br 2 based microemulsion systems, a large number of cosurfactants at the interfacial layer is conducive to the formation of a smaller droplet W/O microemulsion. The effects of n -alkyl alcohols, alkanes, salinity and temperature on the composition and structural parameters of the (C n -4-C n )Br 2 based and C n mimBr based microemulsion systems were also investigated and discussed.