The series does not air on NBC until Oct. 2.
The romantic comedy, which co-stars Ben Feldman ("Mad Men," "The Mindy Project"), is set in the world of an online dating company that details the "A to Z's" of a relationship, from meeting to breakup.
Henry Zebrowski, Lenora Crichlow and Christina Kirk also star in the series.
Milioti has performed on Broadway in The Lieutenant of Inishmore, Coram Boy and Once. She recently starred on "How I Met Your Mother." Her film credits include "The Wolf of Wall Street" and "Sleepwalk With Me."
"A to Z" is executive-produced by Ben Queen, Rashida Jones, Will McCormack, Bill Callahan and Michael Patrick Jann.
The NBC partnership with Clear Channel Media and Entertainment is intended to reach the series’ millennial demographics, which typically watches content online. The partnership will also include on-air and online promotional support for "A to Z" across its contemporary hits radio stations.
The pilot will also be available on NBC, NBC.com, Xfinity, as well as NBC-owned affiliate websites and via cable, satellite and telco providers on demand/online services.
Visit news.iheart.com/AtoZ to watch.
The series will air Thursdays at 9:30 PM. Visit nbc.com/a-to-z for more information.