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James on Monday delivered 32 points, 12 rebounds and 10 assists for the Cavaliers who are finally showing signs of being a NBA contender after a disappointing 1-3 start to begin the regular season.
"I don't care that we all know he can do it," Cavaliers coach David Blatt said of James. "You go out there and have a triple-double and lead your team the way he did, it's easy to overlook that."
Kyrie Irving scored 27 of his 32 points in the second half and Kevin Love drained four three-pointers in the fourth quarter while contributing 22 points for Cleveland, who have won two straight.
The Cavaliers also made good on 13-of-27 three pointers in the win.
Ryan Anderson shot eight-of-12 from beyond the arc and finished with 32 points for New Orleans. He had just nine points at halftime.
Anthony Davis posted 27 points and 14 rebounds and Jrue Holiday finished with 16 points in the loss.
"Our defence got us tonight. We didn't play much," said Pelicans coach Monty Williams. "And our shot selection was poor."
James, Irving and Love all contributed to a 25-7 run that spanned portions of the third and fourth quarters and turned a nine-point deficit into a 94-85 lead with under nine minutes to play. It was the 19th triple double of James' career.