Quantification of inorganic chlorides in crude oil is crucial for the petroleum industry because chlorides can cause corrosion, catalyst poisoning, and pipeline clogging. This work presents an innovative approach using nanoemulsion preparation for the direct potentiometric determination of inorganic chlorides in crude oil samples. The method, termed direct determination of chloride (CDD), uses an oil-in-water (O/W) nanoemulsion to transfer and solubilize inorganic chlorides from crude oil into an aqueous medium. Chloride quantification was performed by direct potentiometric titration of the O/W nanoemulsion. Applied to 15 crude oil samples (API gravity: 13.1-38.2), the proposed CDD method was compared with standard potentiometric titration, as per ASTM D6470, and quantification of chlorides by determining main metals (Na, Ca, and Mg) using flame atomic absorption spectrometry. The proposed method achieved a relative standard deviation below 5 % and a limit of quantification of 0.015 mg g-1. Recovery ranged from 99.0 to 109.2 % for NaCl-added samples and from 97.1 to 99.0 % for those with mixed salts (70 wt % NaCl, 25 wt % CaCl2, and 5 wt % MgCl2). The CDD method showed no statistical differences from ASTM D6470 or flame atomic absorption spectrometry (p < 0.05), confirming that it successfully transfers and solubilizes inorganic chlorides from crude oil samples into the aqueous medium. By integrating nanoemulsion-based solubilization with potentiometric titration, the CDD method provides an accurate and precise technique for the determination of inorganic chlorides in crude oil, with the advantages of simple operation, reduced solvent consumption, and improved sustainability.