An unexpected guest will be there too.
The visit by the reigning NBA champions will coincide with President-elect Donald Trump's meeting with President Barack Obama to discuss the handover of power and transition following a shocking election that left James -- and millions of Americans -- wondering about the future.
Ohio Gov. John Kasich, a onetime Republican presidential rival who refused to endorse Trump and boycotted the Republican National Convention in Cleveland, also was to visit the White House on Thursday.
James had supported Trump's Democratic rival, Hillary Clinton, appearing on stage with the former secretary of state at a campaign rally in Cleveland on Sunday to urge residents to vote.
On Wednesday, just hours after Clinton had conceded the election to Trump, James posted on his Instagram account that he woke up "looking and searching for answers on what has happened." He posted the audio to "Alright," a song by rapper Kendrick Lamar.
The Cavs' trip to Washington, D.C., has been planned for weeks. Coach Tyronn Lue, who received a phone call in June from Obama shortly after Cleveland rallied to beat the Golden State Warriors in the NBA Finals, wanted the visit to happen before the first African-American president left office. Cleveland plays the Wizards at Washington on Friday night.
Lue won back-to-back championships with the Los Angeles Lakers in 2000 and 2001, but he failed to make it to the home of the president of the United States back then. He said it's something he regrets to this day.
"As a young guy [I was] not really respecting what it was and what it meant," Lue said this week. "We won our second championship and I was, what, 22, and I was playing for the Wizards and they came in town, they invited me to go with the Lakers. I just didn't go. It was stupid.
"But I mean, as young guy, you just take things for granted. You don't really understand those opportunities and what that means. Now I'm happy with the fact that years later I'm able to have an opportunity to go again. So I'm going to take full advantage of it."
James has openly expressed his views on numerous political issues in recent years. Following Trump's election, the three-time champion and father of three said he felt the need to offer encouragement to minorities and women.
James wasn't the only Cavaliers player to express his feelings.
J.R. Smith, who also attended Clinton's rally in Cleveland, posted a photo to Instagram of his daughter standing outside the White House.
"How do I even feel confident sending her on play dates knowing the [kid's] family voted for the racist, sexist person, [and] I don't know how they will treat her when she's gone," Smith wrote in the caption. "How? Seriously How?"
Information from The Associated Press contributed to this report.