Ionic liquids (IL) have emerged as a prospective new material for a wide range of industrial applications, owing to their unique structures and properties. Hence, understanding the structure–property relationships of IL is very important for both fundamental and industrial applications. In this study, a series of imidazolium-based IL with different chain lengths, namely C₈mimBF₄, C₁₀mimBF₄ and C₁₂mimBF₄, were synthesized. Their molecular structures were confirmed by proton nuclear magnetic resonance (¹H NMR) and Fourier transform infrared (FTIR) analysis. Thermal gravimetric analysis (TGA) revealed that the IL synthesized were thermally stable in the desired temperature range. Dynamic light scattering (DLS) results of IL was analyzed in order to understand the effect of alkyl length on micellar size. Conductivity and surface tension measurements were carried out to determine the adsorption and aggregation characteristics in aqueous solutions. The influences of temperature as well as alkyl chain length on viscosity were also investigated. Surface adsorption parameters such as surface excess, minimum area, effectiveness and efficiency were also determined from equilibrium surface tension data. A careful analysis of the thermodynamic aspects of air-ionic liquid aqueous systems reveals that free energies of adsorption are favoured over micellization for all systems.