Extensive research has used dimethylarsinic acid (DMA) in urine as a marker of arsenic methylation. The premise is that humans methylate inorganic arsenicals to monomethylarsonic acid (MMA) and DMA and excrete these arsenic species into the urine. However, DMA in urine not only comes from the methylation of inorganic arsenic but also could be a result of metabolism of other arsenic species, such as arsenosugars and arsenolipids. Most environmental health and epidemiological studies of arsenic methylation might have overlooked confounding factors that contribute to DMA in urine. Here we critically evaluate reported studies that used methylation indexes, concentration ratios of methylated arsenicals, or the percentage of DMA in urine as markers of arsenic methylation efficiency. Dietary intake of arsenosugars potentially confounds the calculation and interpretation of the arsenic methylation efficiencies. Many studies have not considered incidental dietary intake of arsenosugars, arsenolipids, and other organic arsenic species. Future studies should consider the dietary intake of diverse arsenic species and their potential effect on the urinary concentrations of DMA.