Lee Jae-Yong, the vice-chairman of Samsung Electronics, was brought into the Seoul Central District Court bound and handcuffed.
Lee, who was arrested in February, has been charged with offering nearly $40 million to the now-impeached president and her close friend Choi Soon-Sil, allegedly as bribes to secure policy favours.
Four other Samsung executives have also been charged.
Special Prosecutor Park Young-Soo said in his opening statement that Lee's case is "one of the most deep-rooted and typical cases involving unhealthy relations between politicians and businessmen".
"In the course of providing bribes, Lee Jae-Yong embezzled company money, illegally diverted domestic assets abroad, hid illegally-earned incomes and committed perjury at parliament," the prosecutor said.
"The Choi case has left a deep scar in history but it has also provided momentum to re-establish the rule of laws by dint of people's power," the prosecutor said.
Ousted president Park Geun-Hye was thrown into jail last week after a court ordered her arrest in connection with the sweeping corruption scandal that brought millions of people onto the streets and saw her impeached.
Her close confidante Choi is also on trial for leading Park to force top South Korean firms, including the tech giant, to "donate" nearly $70 million to non-profit foundations, which Choi allegedly used for personal gain.
