Hudson will appear in multiple episodes as Veronica Moore, a Tony Award-winning Broadway star who has an impact on the lives of Karen (Katharine McPhee) and Ivy (Megan Hilty), TVLine reports.
Smash follows two singers (McPhee and Hilty) who compete for the starring role in a Broadway musical based on the life of iconic star Marilyn Monroe.
Chairman of NBC Entertainment Robert Greenblatt said of the new cast member: "This series is a showcase for some of the best musical talent in the business and that's a fitting description for Jennifer Hudson.
"Her character will represent someone who reached their Broadway dream but also paid a price for it."
Hudson will make her debut when Smash returns for its second season in 2013.
"First Dreamgirls, now Smash," executive producer Steven Spielberg said. "I have no doubt Jennifer will continue to deliver even more inspiration to the audience responsible for giving us a second season on NBC."
Hudson has previously taken home the 'Best Supporting Actress' Oscar for her role in Dreamgirls.
Watch the music video for Jennifer Hudson's 'No One Gonna Love You' below: