James, a four-time NBA Most Valuable Player, was named an All-Star starter for the 20th consecutive year, a streak that began in 2005, his second NBA campaign.
James, a four-time NBA champion, broke the record for All-Star appearances that he had shared with another Lakers legend, Kareem Abdul-Jabbar.
The NBA All-Star Game will be played on February 18th at Indianapolis between elite squads from the Eastern and Western Conference.
As the top West point-getter, James will serve as captain and join a starting lineup that also includes Phoenix's Kevin Durant and Serbian centre Nikola Jokic, a two-time MVP from the defending champion Denver Nuggets.
West guards included Slovenian Luka Doncic of Dallas and Oklahoma City's Shai Gilgeous-Alexander of Canada.
Greek star Giannis Antetokounmpo of the Milwaukee Bucks was named captain for the East, whose frontcourt starters also include Cameroon's reigning NBA MVP and this season's top scorer Joel Embiid of the Philadelphia 76ers and Boston's Jayson Tatum.
"You never want to take it for granted," Tatum said. "For the fans to consistently vote me in is truly an honour. I grew up wanting to be in All-Star weekend every year and to live out that dream in real time is pretty cool. I'm very grateful."
East guards included Indiana's Tyrese Haliburton, the NBA assists leader, and Milwaukee's Damian Lillard, making his eighth All-Star appearance after being traded from Portland to the Bucks before this season.
Fan balloting to determine starters ended last Saturday. Fan votes counted 50% with a media panel and NBA players each counting 25%.
The All-Star Game reverts to an East versus West format after several years where two top vote-getters were named captains and drafted lineups from among other top vote-getters.
Reserves for both teams will be announced next Thursday, with all 30 NBA coaches selecting two guards, three frontcourt players and two others at any position from their respective conference.
NBA commissioner Adam Silver will select the replacement for any player unable to play in the All-Star Game, selecting a substitute from the same conference.
