The singers had been pitted against each other by mentor Cee Lo Green in the final battle, which saw them taking to the stage for a performance of Lady Antebellum's 'Need You Now'.
"Isn't he cute? I sort of have a little crush on Curtis and it kind of broke my heart a little bit that we had to go up against each other but it's the name of the game. Love hurts!" said Emily during her one-on-one time with Cee Lo and his advisor Monica.
Curtis said: "Me and Emily have gotten pretty close and we've become pretty good friends. This is one of those places where there is one loser and one winner and it will suck sending somebody home you've been hanging out with."
Cee Lo had advised the pair that the song was about love but they had to bring the idea of a "volatile relationship" to the table and "reenact the risk of loving someone and losing someone and the chance you take with love".
Curtis and Emily then surprised all of the mentors by ending their battle round performance with a kiss. "One of you is going home!" said host Carson Daly. "Not alone I guess..."
In the end, it was Emily who was sent home by Cee Lo, meaning Curtis became the final member of Cee Lo's team for the live rounds.
The Voice continues next Tuesday at the new time of 9/8c on NBC.
> The Voice recap: The fourth battle round
Watch Emily Valentine and Curtis Grimes kiss on The Voice below: