In this study, a background electrolyte capable to separate and quantify inorganic cations in high ionic strength samples by UV-absorption indirect detection was designed. In this regard, the four most abundant monovalent and divalent cations in earth crust (K+, Na+, Ca+2, Mg+2) were selected as model compounds. A group of small carboxylic acids and, several toluidines and pyridines were evaluated as mild strength complexing agents and chromophoric probes, respectively. The optimized background electrolyte was composed of 200 mM 2,4,6-trimethylpyridine as the chromophoric probe, 250 mM lactic acid as the weak complexing agent and pH buffering reagent (adjusted to pH 4.5), and 5% v/v methanol as organic solvent modifier. Based on a minimum number of components, it provided outstanding separation performance in less than 4 min in a wide linear dynamic range (10 - 2500 µg·mL−1). Performances were contrasted against a reference method based on conductometric detection. Furthermore, studies of separation efficiency and peak shape were carried out at different analyte concentrations in high electric conductivity solutions. The herein developed method demonstrated exceptional features in terms of limits of detection (~10 µg·mL−1), resolution, speed of analysis, sensitivity and peak capacity in high electric conductivity samples. Moreover, the method was successfully applied to high ionic strength samples such as rock digest, sea water, soy sauce and isotonic drinks.