In total, nine City players featured for Team GB at the Sapporo Dome.
Ellie Roebuck, Lucy Bronze, Steph Houghton, Keira Walsh, Caroline Weir, Georgia Stanway, Lauren Hemp and White were all selected in Hege Riise's starting XI, while Jill Scott was introduced from the bench late on with Demi Stokes was an unused substitute.
All made significant contributions in a performance capped by striker White’s clinical double with City colleague Hemp and Bronze providing the assists for her twin strikes.
With Canada and hosts Japan drawing in Wednesday’s other Group E encounter, the result put Team GB in a strong position after Matchday One.
And, as she looked ahead to Saturday’s encounter with Japan, White asserted that the side were ready to kick on again.
“As a squad, I feel we can still grow and get better as the tournament goes on,” White declared.
“Collectively as a whole squad and staff, we’ve worked tremendously hard up to this moment and I feel proud of the whole squad.
“There are still things we need to work on but we are really pleased with the three points.
“But it doesn’t stop here for us, we are now really looking forward to facing Japan.”
The two goals were also the latest landmarks in White’s magnificent individual career.
A consistent scorer for both City and England’s Lionesses, White admitted opening her Olympic account was another proud moment.
"It felt amazing [to score twice]. I feel really proud to be part of Team GB and scoring and contributing to the team felt amazing,” she reflected.
“I’m obviously delighted to contribute to the team winning and to score two goals.
"We had total respect for Chile and what they could bring to the game. We wanted to focus on what we could do and there were moments when we had really great play.”
Next up, Team GB tackle Japan on Saturday morning, kick-off 11.30am (BST).
While it was the perfect start for City’s British contingent, American defender Abby Dahlkemper and Canadian winger Janine Beckie will be looking to help the USA and Team Canada respond respectively in their second group matches.
World champions the USA succumbed to a shock 3-0 defeat at the hands of Sweden to suffer a first loss in 44 games in Wednesday’s Group G opener.
Dahlkemper played the full 90 minutes but was powerless to prevent the 2016 Olympic silver medallists from securing all three points.
It’s a result that left the USA bottom of Group G and seeking an instant response in Saturday’s now crucial second matchday clash against New Zealand who are also without a point after a 2-1 loss to Australia.
Beckie and Canada meanwhile had to settle for a point in their Group E opener with Japan who claimed an 84th minute leveller to cancel out Christine Sinclair’s early strike and so earn a 1-1 draw.
The result left Canada, bronze medallists at both the 2012 and 2016 Olympics, second in the table on one point ahead of Saturday’s second Group E clash against Chile.