The couple's chemistry could be felt as they delivered a romantic, fireside rendition of their duet, "Nobody But You," on the ACM Presents: Our Countryspecial on Sunday night.
Shelton, 43, and Stefani, 50, brought the passion to the performance, which was filmed in Oklahoma by Stefani's brother.
"We happen to be in Oklahoma, hiding away from everybody, doing what we're supposed to do. And, we're also doing what I think everybody else must be doing, which is... drinking all day," Shelton said.
"Not me! What are you talking about," Stefani replied with a laugh as she set down her wine glass.
"We planned to perform at the ACM Awards tonight, and clearly that's not happening. We wanted to sing this song there, but we're here. Let's do it here. You want to?" Shelton asked Stefani, who responded with a kissy face and "Mm-hmm."
The couple -- who gazed into each other's eyes throughout the performance -- was just one act in a star-studded lineup for the two-hour virtual show, which also featured conversations and a look back at past ACM Awards moments.
ACM Presents: Our Country aired in place of the ACM Awards, which was recently postponed due to the coronavirus pandemic. During an interview with ET's Kevin Frazier, the night's host, Gayle King, opened up about how the special came together.
"We were all ready for the big night [in] April, but the coronavirus changed everything," she said. "The genius of this is that all the superstars of country music [have] done special performances from their home that they shot themselves. So, you've got Lady Antebellum [at] one, two, three different locations. You've got Blake and Gwen fireside in Oklahoma singing ‘Nobody But You’ with her brother doing the camera."
King added that she thinks the special reflects how country musicians are some of the "kindest, most humble, nicest, most generous" humans.
Sunday's special was designed to be "filled with entertainment, hope and reflection, bringing the healing power of music to Americans at a time when they need it most," the Academy of Country Music said when it first announced the event.
ACM Presents: Our Country airs on Sunday April 5 at 8 p.m. PT/ET/7 p.m. CT on CBS and also streams on CBS All Access for subscribers -- you can sign up for that here. You can also watch on Hulu with Live TV, YouTube TV and AT&T Now if you're a subscriber to one of those services, all of which offer a 7-day free trial.