The percutaneous penetration of 2,4‐dichlorophenoxyacetic acid (2,4‐D) and 2,4‐D dimethylamine salt (DMA) was evaluated separately in five male volunteers who participated in both experiments. Urine samples collected for 144 h following dermal applications of 10 mg to the dorsum of the hand (9 cm2) were analyzed for 2,4‐D. Following the acid application, an average of 4.46 ± 0.849% was recovered in the urine and a significantly lower amount of 1.76 ± 0.568% following the DMA application. Significantly higher amounts of 2,4‐D DMA (7.68 ± 0.493 mg) were washed off the hand 6 h following application as compared with 2,4‐D acid (5.35 ± 0.384 mg). These results indicate that, in addition to the differences in physical and chemical properties of the two compounds that will affect absorption, the amount of the chemical absorbed is related inversely to the amount of washed off. Urinary excretion of 2,4‐D was not complete in all volunteers 144 h following either application, but in all cases it was approaching the limit of detection. An average of 84.8 ± 2.55% and 76.8 ± 8.05% of the total recovered in 144 h was recovered in the urine 96 h following 2,4‐D acid and 2,4‐D DMA application, respectively. Average, approximated half‐lives for excretion were 39.5 ± 8.1 h for the acid application and 58.5 ± 13.2 h for the DMA application.