The world's top chip and smartphone maker declined to say how many people might be compensated, but around 40 employees have filed claims with the state Korean Workers' Compensation and Welfare Service in the past six years.
In a statement, Samsung CEO Kwon Oh-Hyun said the company would provide "proper compensation" to those affected and the families of some employees who had died.
(Also see: South Korea says Samsung chip plant caused cancer)
"We've failed to pay careful attention to the pain and difficulty of them and their families," he said in a statement, vowing to set up a neutral arbitration group to arrange fair settlements.
Samsung has always rejected the charge that the cancers resulted from workplace exposure to toxic chemicals, and Kwon's statement included no acceptance of responsibility for the employees' condition.
Previously Samsung has pointed to independent studies that found no link between its workplace environment and employee illnesses.
Public interest in the dispute grew in February with the release of "Another Promise", a film based on Hwang Yu-Mi a real-life employee who died in 2007 of an acute form of leukaemia after working for four years at one of Samsung's semiconductor plants.
For legal reasons, Samsung was not named in the film but the title was a clear echo of a well-known Samsung slogan "Another Family".
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