The former Today star will play herself, as a talk show host assigned to grill Baldwin's controversial newspaper columnist character. Warren Leight, the show's executive producer, says the "chemistry on screen" between the two "is palpable."
Couric, 57, signed a record $40 million contract with ABC in 2011 for her talk show Katie, but the show has since been cancelled. Episodes will continue to air through June of this year.
Her fellow guest star Alec Baldwin will appear on the show despite having recently announced his intent to leave public life.
The episode, set to air March 19, will mark longtime SVU star Mariska Hargitay's directorial debut.