Recovery studies using water samples fortified with 30–350 ng/L of α‐, β‐γ‐,and δ‐hexachlorocyclohexane (HCH) isomers using the Kuderna‐Danish evaporators and modified Synder column were carried out. These studies consisted of extraction, concentration and analysis by two operators on five different mixed concentrations of the four isomers with five replicates on three different days. The mean % recoveries (± standard deviation) of 98.02 ± 7.27 for the α‐, 96.61+4.88 for the β‐, 96.59+5.72 for the γ‐and 73.89 ± 11.20 for the δ‐isomers were observed. The analysis of variance between concentrations for operator 1 shows that the F ratio is significant for the isomers α‐, γ‐(p < 0.05). However, in the case of operator 2, there were significant differences between concentrations only in the case of the α‐isomer. It has also been shown that there were significant differences in operator variability for the α‐, γ‐, and δ‐isomers and that operator 2 with minimum experience could obtain consistent recoveries with β‐γ‐and δ‐HCH isomers with greater than 95% confidence. Further, a method has been described for purifying recovered hexane solvent.