The three-time Grammy winner will perform alongside Shelton from his Oklahoma ranch on the Grand Ole Opry on Saturday, May 9.
Also performing that evening will be Dustin Lynch and Trace Adkins from the Opry House in Nashville.
The show, hosted by Bobby Bones, will stream live on the Circle All Access Facebook page beginning at 8pm CT.
Earlier this week, Stefani took to social media to share her excitement over her first chart-topping country single.
Trying to wrap my head around the fact that I even get to know you Blake Shelton, let alone be on Such a beautiful classic duet w u,” she wrote. “Thank you for taking me along on this ride with you!! I am so grateful and blown away by all the support everyone has shown us!!?!!”
The show will be the Opry’s 4,923rd consecutive Saturday night performance.