The firm is accused of giving large donations to non-profit foundations operated by Choi Soon-sil, a close confidante of Ms. Park.
The donations were allegedly given in exchange for political support of a controversial merger.
Ms. Choi has been charged with coercion and attempted fraud.
According to South Korea’s Yonhap news agency, Choi Gee-sung, a Samsung vice chairman, and Chang Choong-ki, a president at the group, were being interviewed on Monday by special prosecutors about the corruption allegations.
It was reported the pair were being treated as witnesses, rather than being suspected of any wrongdoing.
The claims circle around a merger between the electronics giant’s construction arm, Samsung C&T, and an affiliate firm, Cheil Industries.
The deal went through despite significant opposition from shareholders, who said it would hurt minority shareholders while benefiting the family of Samsung’s group owner Lee Kun-hee.
South Korea’s National Pension Service (NPS), which owns stakes in both companies, sealed the deal by voting in favor of it and the head of the NPS has since been arrested.
But prosecutors also allege that Samsung gave €2.8m euros ($3.1m; £2.5m) to a company co-owned by Ms. Choi and her daughter, in return for Ms. Park’s support for the deal.
In a parliamentary session last month, senior executives of Samsung admitted the firm gave money to help the equestrian career of Ms. Choi’s daughter, Chung Yoo-ra.
Samsung’s de-facto head, Lee Jae-yong confirmed that the company had paid for a horse for Ms. Chung – though to be worth around $850,000 – saying he regretted the move.
A total of eight firms have so far admitted donating funds linked to President Park Geun-hye, but deny seeking favors.
Politicians voted on 9 December to impeach President Park – a decision South Korea’s constitutional court has six months to uphold or overturn. Until then she remains formally president but stripped of her powers, which are handed to the prime minister, a presidential appointee.
Ms. Park denies wrongdoing but has apologized for the way she managed her relationship with Ms. Choi, who also denies committing criminal offenses.