Shelton, 39, and Stefani debuted their new duet "Go Ahead and Break My Heart" on "The Voice".
The Country crooner said the chemistry in the duet came from developing the song together, reported ET online.
"When I originally started writing this song that we're performing tonight, I was only trying to impress Gwen.
"I started this song and wrote about half of it and sent it to her and she wrote the other half of it. It was just kind of something for she and I to help us feel better about what we were going through," Shelton said.
"The hardest part was not smiling throughout the whole thing while we're singing it because we can't believe this is happening. We still can't believe this is happening. It's cool to be witness to something that's this honest and fun," he said.
The singer also admitted that he "learned a lot" about creating songs from the 46-year-old No Doubt frontwoman.
"I used to just love (her) songs that I heard on the radio and I didn't really know the stories. All these songs you know by her, whether it was her solo stuff or (from her) album, she's just telling you something that just happened to her.
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