It was the team’s biggest ever win, beating the previous record of 13-0 against Hungary 16 years ago.
White went into the match needing two goals to take her past Kelly Smith’s previous record of 46 goals, and that took her just nine minutes. The 32-year-old went on to complete her hat-trick.
She was one of four hat-trick-scorers on the night - Lauren Hemp netted four times, while Beth Mead and substitute Alessia Russo also registered trebles.
Beth England notched a brace, and there were also goals from Ella Toone, Georgia Stanway, with a penalty, Jess Carter, Jill Scott and Jordan Nobbs on a historic evening for the Lionesses, who were 8-0 up at half-time.
It was a sixth win from six Group D games for England, their first six fixtures under Sarina Wiegman which have seen 43 goals scored and none conceded.
After breaking the goalscoring record, White said: “I actually feel really emotional about it. It’s been spoken about for a long time and I feel very proud.
“I feel really proud of the girls tonight, we’ve got so many girls who scored their first goal for England.”
Having seen her side beat Latvia 10-0 in Riga last month, Wiegman spoke in the build-up to this encounter of wanting another “ruthless” performance from England - and that is certainly what followed.
Mead got things started with a third-minute finish, shortly after Alex Greenwood had cracked a shot against the crossbar.
White then equalled Smith’s mark in the sixth minute with a wonderful strike from just outside the box, before breaking the record three minutes later by slotting in from close range, with Stanway assisting for both goals.
There was no let up for Latvia - 94 places below England at 102nd in the world rankings - as Mead registered her second of the contest in the 12th minute and Hemp headed home in the 18th for her first international goal. Mead then completed her hat-trick with a header another five minutes later to make it 6-0.
Some respite for the visitors followed, before a Toone strike and Hemp header arrived in quick succession just before half-time to see Wiegman’s side go in 8-0 up.
White’s hat-trick was sealed four minutes into the second half when she fired a shot from the edge of the area that goalkeeper Laura Sinutkina could not prevent going through her hands.
And England hit double figures three minutes after that, Stanway deservedly getting on the scoresheet with a penalty following a foul on Mead.
The substitutes started getting in on the act with Carter touching home in the 56th minute, Beth England scored again in the 61st, and Scott, also introduced from the bench, then made it 13-0 in the 67th.
That put England level with the score from their biggest win - and that was soon eclipsed as Russo, who had replaced White on the hour, opened her international account with a header to take the team to 14.
The deluge of goals continued with Hemp scoring her third, Nobbs becoming the latest substitute to score, Russo netting twice in two minutes for her hat-trick, and Beth England then registering her second of the game.
The incredible rout was then completed in the 88th minute as Hemp got her fourth to make it 20-0.
Additional reporting by PA Sport.