Cleveland Cavaliers set up their third straight NBA finals appearance against Golden State Warriors with a 135-102 win over Boston Celtics.
James, 32, surpassed Chicago Bulls legend Michael Jordan as the all-time leading scorer in the play-offs.
The Warriors swept San Antonio Spurs 4-0 in the Western Conference finals.
They were crowned NBA champions in 2015 but were defeated last year as Cleveland's 52-year wait for a major sporting title came to an end.
Game one of the NBA Finals takes place at the Warriors' Oracle Arena in Oakland on Thursday, 1 June (02:00 BST on Friday).
Cavs small forward James hit a three-pointer from the left wing in the third quarter to pass Jordan's record of 5,987 play-off points, which had stood for 19 years.
James, who is chasing his fourth NBA title this year, finished with 35 points in the game to set a new mark of 5.995 points in 212 play-off games, while six-time NBA champion Jordan set his record in 179 games.
He has scored 955 of those points against Boston, the most for any player against any team.
Victory secures a seventh consecutive NBA Finals for James, winning two titles in four appearances with Miami Heat between 2011 and 2014, before returning to home-town team Cleveland.
The Cavs also set a franchise record for most points in a quarter in the play-offs by recording 43 in the first quarter of game five against the Celtics.
Report by Miyen Akiri
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