The Manchester City striker scored twice in the opening 10 minutes of Tuesday night's Women's World Cup qualifier at Doncaster's Keepmoat Stadium to eclipse Kelly Smith's mark of 46.
The 32-year-old, winning her 101st cap, equalled the record with a long-range strike before breaking it just three minutes later.
And she completed her treble for good measure early in the second half with an effort from the edge of the area.
White, won her first cap in 2010, scoring in a win over Austria, and has developed into a key member of an England side which has reached back-to-back World Cup semi-finals.
She was the joint top-scorer at the 2019 tournament with six goals.
On the club front, White won two Women's Super League titles with Arsenal in 2011 and 2012 and went on to play for Notts County and Birmingham before joining Manchester City in 2019.
White's City and England team-mate Steph Houghton, currently out injured, said in a video message on the club's Twitter account: "Ellen White, what can I say - absolutely unbelievable person and absolutely unbelievable player.
"You thoroughly deserve it because of all the hard work you've put in on and off the training pitch. You're an amazing team-mate and also an unbelievable best friend."
On breaking the scoring record, White said on ITV4: "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."
Asked what she would have said if told as a schoolgirl she would one day become England's record goalscorer, White said: "I'd say you're having a laugh! It's incredible. But I'm not stopping here. I still want to score goals for England."
White also paid tribute to Kelly Smith, saying: "To me she's a legend, I have so much love and respect for her. She'll always be the best for me."