Taking place at Caja Magica, the 17th annual EMAs will be broadcast live Nov. 7 on MTV platforms.
The show's lineup of performers includes Kings of Leon, Ke$ha, Kid Rock, Katy Perry and Linkin Park.
MTV said it will release the names of additional performers and presenters at a later date.
"I am so excited to host the 2010 EMAs in the beautiful and sexy city of Madrid!" Longoria said in a statement. "I can't wait to see some fabulous performances and I am so proud that the two most nominated artists this year are two amazing women -- Lady Gaga and Katy Perry -- who are making some of the most exciting music in pop right now."
"Madrid, watch out," Ke$ha said. "I'm coming to party and I promise it will be messy."