The reshuffle, announced at an annual general shareholders' meeting, leaves the company with three joint CEOs.
Boo-Keun Yoon, head of the huge television unit, and mobile division chief J.K. Shin will become co-CEOs with Kwon Oh-Hyun, who will also retain his position as Chairman of the Board of Directors.
The promotions were announced as the world's biggest technology company by revenue unveiled its latest flagship Galaxy S4 smartphone in New York City.
A company statement noted that under Yoon Samsung's TV business retained its global leadership position, while Shin oversaw the mobile division's surge to the top of the world rankings in the smartphone and overall mobile phone sectors.
Yoon will continue his stewardship of the consumer electronics division, which includes TVs and appliances, while Shin will remain in charge of the IT and mobile communications business, it said.
"The new leadership structure will serve to clarify and enhance independent management of the two set divisions," the statement added.