A new Korean standard for the determination of Cr(VI) in soils has been officially published as ES 07408.1 in 2009. This analytical method is based on the hot alkaline digestion and colorimetric detection prescribed by U.S. EPA method 3060A and 7196A. The hot alkaline digestion accomplished using 0.28 M $Na_2CO_3$ and 0.5 M NaOH solution (pH 13.4) at $90{sim}95^{circ}C$ determines total Cr(VI) in soils extracting all forms of Cr(VI), including water-soluble, adsorbed, precipitated, and mineral-bound chromates. This aggressive alkaline digestion, however, proved to be problematic for certain soils which contain large amounts of soluble humic substances or active manganese oxides. Cr(III) could be oxidized to Cr(VI) by manganese oxides during the strong alkaline extraction, resulting in overestimation (positive error) of Cr(VI). In contrast, Cr(VI) reduction by dissolved humic matter or Fe(II) could occur during the neutralization and acidic colorimetric detection procedure, resulting in underestimation (negative error) of Cr(VI). Futhermore, dissolved humic matter hampered the colorimetric detection of Cr(VI) using UV/Vis spectrophotometer due to the strong coloration of the filtrate, resulting in overestimation (positive error) of Cr(VI). Without understanding the mechanisms of Cr(VI) and Cr(III) transformation during the analysis it could be difficult to operate the experiment in laboratory and to evaluate the Cr(VI) results. For this reason, in this paper we described the theoretical principles and limitations of Cr(VI) analysis and provided useful guidelines for laboratory work and Cr(VI) data analysis.