Jeffrey Pollack had been chief marketing and strategy officer and special advisor for the Chargers.
He also has held executive and communication positions with the NBA, NASCAR, the World Series of Poker and the Professional Bull Riders.
The XFL is being re-launched by professional wrestling executive Vince McMahon. The football league was first launched as an alternative to the NFL in 2001, playing just one season before closing amid revenue losses.
McMahon is planning to bring the league back in 2020.
The league's first commissioner and chief executive will be Oliver Luck, a former college sports executive who played five years in the NFL as quarterback. His son is quarterback Andrew Luck of the NFL's Indianapolis Colts.
"It's not often that a new professional sports league is positioned for success like the XFL," said Pollack. "There's a clear vision for what we will offer our fans, players and partners, and I look forward to working closely with Vince and Oliver to bring that vision to life."
In Los Angeles the XFL team will play at Dignity Health Sports Park, formerly the StubHub Center, in Carson.
The Chargers play there now, but they are expected to move into the new stadium under construction in Inglewood slated to open in 2020, which they will share with the Rams.
The other cities with XFL teams will be Dallas, Houston, New York, St. Louis, Seattle, Tampa Bay and Washington D.C. The league will have a 10-week regular season schedule, with two semifinal playoff games and a championship.