She replaces Hermes Tang, who is retiring, as the leader of the 7,800-strong department.
Ho, wife of constitutional and mainland affairs minister Erick Tsang, joined customs as an inspector in 1991 and rose through the ranks.
She was promoted to deputy commissioner in 2019.
Chief Executive Carrie Lam said Ho possesses “extensive experience in departmental operations”, and she’s confident that the new commissioner will lead the department in meeting the challenges ahead.
As for the outgoing commissioner, the CE said Tang had “made sustained efforts” in tackling smuggling and drug trafficking activities, as well as in upholding Hong Kong’s trading integrity.
Tang was recently mired in a controversy that led him to apologise to the public.
He was fined for flouting social distancing rules after he and two other senior officials were caught having a hotpot dinner with several others in March at a luxury club.