The Manchester City striker struck in each half to give Team GB a winning start to their campaign in Japan.
That Hege Riise’s side failed to add to the scoreline owed much to their own profligacy and desperate, last-ditch defending from Chile.
They now face the host nation in Sapporo on Saturday before playing Canada in Kashima to complete Group E next Tuesday.
After Maria Jose Urrutia shot wide for Chile early on, Team GB took control in Sapporo and were denied an opener by the offside flag after 11 minutes.
White turned in from close range when Christiane Endler parried Georgia Stanway’s low effort but the striker’s celebrations were correctly cut short.
But Team GB did not have to wait long as White opened the scoring after 18 minutes.
The side – primarily made up of England players – had played just one warm-up game together and, Riise was delighted with their display. She said: “We have been waiting for this game a long time and we were so eager to get started. Get a good start, get a win, keep them away from our goal, score two goals it’s a good statement for the games coming up. How we started the game was exceptional.
“The first 30 minutes were the best we’ve played and we kept it going. It wasn’t pretty for the whole game but we fought and we managed to get the result we wanted. I asked for a good start and we had a great one.”
Riise, who won gold as a player with Norway in 2000, also reserved praise for Manchester City’s White. She added: “We trust Ellen to score goals and she does. Not only goals, she fights hard, she works for 90 minutes to get the goal or other players in. She’s important and brings a lot of confidence to this team. It’s a team effort and we really stood out. We are so happy with the squad we have. We can put players on and make a difference and that’s the quality we want.”
Lucy Bronze’s deep cross was nodded back by Lauren Hemp and White finished from six yards.
Riise’s side were a constant threat with Stanway having a shot blocked while Hemp and Millie Bright fired off target.
Chile had been outplayed, especially in midfield, and Kim Little was thwarted as Team GB chased a second when her shot was blocked in first-half stoppage time.
Team GB continued their dominance following the break and Hemp shot over after a neat move before Chile survived a VAR scare when Carla Guerrero appeared to take out White, only for the forward to be ruled marginally offside.
Chile offered no threat, with Ellie Roebuck a second-half spectator in goal, and White sealed victory with 17 minutes left.
Her flick was laid off to Bronze by Nikita Parris and the Manchester City player crossed for White to acrobatically volley in from six yards.
Rachel Daly shot at Endler but there was little need for Team GB to push with the game already won.
Chile boss Jose Letelier said: “We knew going into it Great Britain were a very powerful team. In the first half we got good close opportunities which we could have taken advantage of more. We have to be objective and we know Great Britain were better than us in this game.
“We have a women’s team who are still growing and we are going to play our game to our fullest potential. We have to learn from this going forward.”