The compounds 2,4-dichlorophenol (2,4-DCP) and 2,4,5-trichlorophenol (2,4,5-TCP) are classified as priority pollutants, with potentially hazardous impacts on the environment. In soil, dissociation of the phenol group occurs, resulting in the simultaneous presence of neutral phenol and anionic phenolate. Although the toxicity of 2,4-DCP and 2,4,5-TCP to soil microbiota has been suggested to be mainly due to the phenolate anion, this hypothesis cannot be tested due to the lack of appropriate methods of extracting and quantifying the anionic form of these compounds (unlike the neutral form, which can be easily quantified). In this study, we developed a method that enables extraction and quantification of phenolate ions. The method could therefore be used to elucidate the processes that regulate the behaviour of chlorophenolic molecules in soil and to clarify the distribution and toxicity of these compounds in the edaphic environment. The proposed method uses saline solutions (CaCl2, KCl and K2SO4) of low ionic strength to extract the chlorophenolate anion from soil, followed by sequential transformation of the anion from the aqueous solution to an organic solvent that enables subsequent identification and quantification of the molecule by gas chromatography. Two soils of contrasting pH were used to test whether the proposed method was practicable. The method enabled analysis of the distribution of the neutral and anionic forms of the chlorophenols in both types of soil considered and revealed the influence of soil pH in this distribution.