The Manchester City forward, making her 101st appearance for her country, equalled Kelly Smith's record of 106 goals for England after just six minutes at the Keepmoat Stadium.
White, who achieved the mark in 16 games fewer than Smith, surpassed the milestone just three minutes later before adding her third – one of four hat-tricks scored by England on Tuesday – after the interval.
The 32-year-old now has 48 goals for the Lionesses, averaging almost a goal per game, following England's record competitive win. Their 13-0 thrashing of Hungary in October 2005 was the previous biggest margin of victory.
In total England, who had hit double figures 10 times previously since the team started in 1972, had 10 different goalscorers and over their two group matches against Latvia have attempted 121 shots while facing none in return, according to Opta data.
England remain top of their World Cup qualifying group, with a perfect six wins from six games, in which they have managed 53 goals and conceded none in reply.
White is also the second-highest scorer in Women's Super League history, netting 58 times in 126 appearances for Arsenal, Notts County, Birmingham and Manchester City.