We address a novel method for analytical determinations that combines simplicity, rapidity, low consumption of chemicals, and portability with high analytical performance taking into account parameters such as precision, linearity, robustness, and accuracy. This approach relies on the effect of the analyte content over the Gibbs free energy of dispersions, affecting the thermodynamic stabilization of emulsions or Winsor systems to form microemulsions (MEs). Such phenomenon was expressed by the minimum volume fraction of amphiphile required to form microemulsion (Φ(ME)), which was the analytical signal of the method. Thus, the measurements can be taken by visually monitoring the transition of the dispersions from cloudy to transparent during the microemulsification, like a titration. It bypasses the employment of electric energy. The performed studies were: phase behavior, droplet dimension by dynamic light scattering, analytical curve, and robustness tests. The reliability of the method was evaluated by determining water in ethanol fuels and monoethylene glycol in complex samples of liquefied natural gas. The dispersions were composed of water-chlorobenzene (water analysis) and water-oleic acid (monoethylene glycol analysis) with ethanol as the hydrotrope phase. The mean hydrodynamic diameter values for the nanostructures in the droplet-based water-chlorobenzene MEs were in the range of 1 to 11 nm. The procedures of microemulsification were conducted by adding ethanol to water-oleic acid (W-O) mixtures with the aid of micropipette and shaking. The Φ(ME) measurements were performed in a thermostatic water bath at 23 °C by direct observation that is based on the visual analyses of the media. The experiments to determine water demonstrated that the analytical performance depends on the composition of ME. It shows flexibility in the developed method. The linear range was fairly broad with limits of linearity up to 70.00% water in ethanol. For monoethylene glycol in water, in turn, the linear range was observed throughout the volume fraction of analyte. The best limits of detection were 0.32% v/v water to ethanol and 0.30% v/v monoethylene glycol to water. Furthermore, the accuracy was highly satisfactory. The natural gas samples provided by the Petrobras exhibited color, particulate material, high ionic strength, and diverse compounds as metals, carboxylic acids, and anions. These samples had a conductivity of up to 2630 μS cm(-1); the conductivity of pure monoethylene glycol was only 0.30 μS cm(-1). Despite such downsides, the method allowed accurate measures bypassing steps such as extraction, preconcentration, and dilution of the sample. In addition, the levels of robustness were promising. This parameter was evaluated by investigating the effect of (i) deviations in volumetric preparation of the dispersions and (ii) changes in temperature over the analyte contents recorded by the method.