The five repair workers were called in Sunday night to stop the leak of diluted hydrofluoric acid at the plant in the city of Hwaseong, 43 kilometres (26 miles) southwest of Seoul, a Samsung spokesman told AFP.
One was taken to hospital Monday with pains in his throat and chest but died hours later. The remaining four were also treated in hospital but released, the spokesman said.
The leak involved about two to three litres of acid and was contained early Monday morning, he said.
The acid is an acute poison that can damage lungs and bones and affect the nervous system, as well as burn the skin.
"The situation has been contained and Samsung will be investigating the circumstances of this unfortunate incident," the company said in a statement, offering its "deepest condolences" to the dead man's family.
Samsung is the world's top maker of smartphones, memory chips and flat-panel TVs.
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