Florida bartender Jake Barker, 28, showed off a formidable falsetto as he took on Usher's "Climax" in a sexy duet with Georgia's Brittnee Camelle, 23. The singers turned up the heat for Adam Levine, who had stolen both artists from Usher.
"I really didn't expect that from you," Shakira said of Barker's trills and runs.
Levine agreed, noting Barker's inexperience. "It kind of blows me away," he said as he picked Barker. "You seem like someone who has been singing his whole life."
Another singer to turn heads Monday for Blake Shelton's team was Michigan's Ryan Whyte Maloney, 33, who effortlessly helmed Rascal Flatts' "Easy" to outpace Kaleigh Glanton, 23, of Kansas.
"He comes out here every time with this 150 percent confidence," said Shelton.
Team Usher saw two strong battles Monday. New Jersey's Melissa Jiménez surprised some by ousting Washington native Music Box on the Alicia Keys hit "Girl on Fire."
Shelton praised Music Box's energy and presence but said "Melissa is very smooth when she sings and she just glides through there."
Usher also had a tough decision with Virginia's Bria Kelly, 17, and Utah's Madilyn Paige, 16. Their performance of the Pretenders classic "I'll Stand by You" left the judges feeling something was missing.
"I'm not saying it was bad, but I don't think anybody really stood out," Shelton said. Levine agreed: "I was left desiring more."
Usher finally settled on Kelly, but at the last minute, Shelton used his only steal to pull Paige onto his team. "I believe in you as an artist," he told Paige. "Now we've just got to make a performer out of you."
The steal caught Usher by surprise. "I'm a little scared. I ain't gonna lie, man," he told Shelton.
The night's lone battle for Team Shakira saw Los Angeles native Dani Moz, 26, beat out another power singer, Clarissa Serna, 27, of Texas, on the Pink anthem "Perfect."
"Dani, you were unwavering," Usher enthused. "That is something that can't be taught, to understand how to be a star." Added Shakira: "I think you have amazing potential."
Team Adam saw a tough decision with the pairing of Austin, Texas, indie duo Dawn & Hawkes against Minnesota rocker Kat Perkins, 30, on KT Tunstall's "Suddenly I See." While Dawn & Hawkes were light and airy, Perkins seized her solo moments to raise the energy level and shine.
Shelton took note. "As good as Dawn & Hawkes sound, I found myself watching Kat. It was almost like they were watching Kat."
In the end, Levine chose Perkins, saying, "You are one of the most underrated singers of the competition."
The final 20 contestants head into the playoff round Tuesday (8 p.m. ET), where they will sing solo. During the playoffs, each coach will have to dump two singers, narrowing the field to 12 for the live rounds.