The three-time National Basketball Association champion, who recently signed with the Los Angeles Lakers, told Lemon he thought the president was using sports to divide the country.
Trump happened to see the interview on Friday, and the president blasted both James and Lemon in a tweet posted just before midnight.
Trump also suggested he prefers basketball legend Michael Jordan to James, a possible reference to the keen debate about which of the two men is the better player.
"A man who puts kids in classrooms or one who puts kids in cages?" tweeted Lemon, who also added a sarcastic #BeBest, which was a nod to Melania Trump's initiative to encourage children to be their best selves.
James told CNN earlier this week that he would "never" sit across from Trump, but would sit down with former President Barack Obama. Trump's remarks included his belief that Michael Jordan was the superior player. Trump tweeted in 2013 to call James a "great guy" after he won 2013's Athlete of the Year ESPY award.
In choosing her official first lady platform, Trump picked something that involved teaching kindness on social media, something her husband clearly does not practice, even though she continues to face widespread criticism for that decision amid cries of hypocrisy. James tweeted at the time. "Maybe you'd like to talk about the 160,000 kids who skip school every day for fear of being bullied, or that 280,000 students are physically attacked in schools every month", Grisham told CNN.
Since Mrs. Trump's initial comments about James, which she delivered through her spokesperson, a senior White House official has insisted that the First Lady was in no way picking sides by praising James for his charity work.
This weekend's controversy was just the latest in a long-running feud between James and Mr Trump.
Cleveland Cavaliers forward LeBron James (23) tries to pass the ball against Golden State Warriors guard Stephen Curry (30) during the third quarter in game four of the 2018 NBA Finals at Quicken Loans Arena.