The Ukrainian will be joined by female assistants and compatriots Maryna Striletska and Svitlana Grushko for the World Cup qualifier at the Estadio Nacional de Andorra.
The trio were all involved in Copenhagen's 3-1 win over Lincoln Red Imps last Thursday in the Europa Conference League.
France's Stephanie Frappart, who refereed the 2019 Super Cup between Liverpool and Chelsea, will be the VAR for the Three Lions' clash.
Frappart reached another historic landmark by becoming the first woman to referee a men's World Cup qualifying match back in March.
The 37-year-old officiated the Netherlands' 2-0 win over Latvia days before Monzul oversaw Austria's 3-1 victory against Faroe Islands.
Monzul, 40, however became the first woman to take charge of a senior men's international game year.
Monzul, who has been refereeing in the men's Ukrainian Premier League since 2016, was in the middle for the Nations League clash between San Marino and Gibraltar.
She has also refereed at four Women's World Cups, including the final in 2015 when the United States beat Japan 5-2.
Monzul - who speaks fluent English - took charge of her first international match back in September 2005 and has risen up the ranks since.
The highly-acclaimed official was in charge of Great Britain's Women's side's 1-1 draw with Canada at the Tokyo Olympic Games this summer.
The fourth official and assistant VAR for England's away fixture against Andorra are both male - Denys Shurman and Viktor Matyash respectively.
Pierluigi Collina, chairman of FIFA's referees committee, publicly spoke when Monzul and Frappart were announced for the March fixtures.
He said: "FIFA will continue to champion the development of female refereeing and I'm confident that the appointment of female match officials to men's games will be absolutely commonplace in the future."