"It's a fresh, exciting time for the team and I'm looking forward to seeing how we can develop together at the start of this new era for England women's cricket."
Head coach Mark Robinson, who recently lost the services of Sarah Taylor to an 'indefinite break', has praised his new skipper's "superb work ethic, integrity and commitment."
Knight has played five Tests, 33 Twenty20s and 55 one-day internationals for her country.
Seamer Anya Shrubsole has been named as the team's vice-captain.