Lukaku became Belgium's all-time top goalscorer at the age of only 24 as he grabbed the winner in their 1-0 friendly victory over Japan.
Having also scored twice in a draw with Mexico, the Reds number nine nodded in the winner on 72 minutes to eclipse Paul van Himst and Bernard Voorhoof at the top of the Belgian goalscoring charts.
It was his 31st goal for the other Red Devils, and with many years still ahead of him, Lukaku will continue to plunder the goals for Belgium - his is a record that may stand unsurpassed for decades to come.
Roberto Martinez's dominant men - with Marouane Fellaini also key - won nine out of their 10 qualifying games and will be dark horses for a strong showing in Russia.
Rashford, meanwhile, played the last half an hour in England's 0-0 draw with world champions Germany on Friday.
Selected to start in Tuesday's meeting with Tite's top-ranked Selecao, Rashford did himself huge credit on a night of experimentation for England and Southgate.
Rashford showed the fearless streak for which he is so admired, with his constant willingness and determination to run at Brazil's defence, and went close with two first-half efforts in an otherwise attritional affair.
His pace, skill and fleet of foot would not have looked out of place in the ranks of England's illustrious and star-studded opponents.
Jesse Lingard also featured in both games, and Ashley Young made his first appearance for the national team since 2013 with an appearance as a late substitute against Brazil.
Elsewhere, Victor Lindelof played in both ties as Sweden edged out Italy in the play-offs for a slender 1-0 aggregate win, a result that means the Azzuri (and Matteo Darmian) will miss a first World Cup finals since 1958.
Paul Pogba and Anthony Martial ensured that France pipped the Swedes to the automatic place, but the Netherlands, with Daley Blind and recent Dutch debutant Tim Fosu - Mensah, failed to make it.
2010 winners Spain - with David de Gea, Juan Mata and Ander Herrera - comfortably qualified from Group G under Julen Lopetegui and will head to the World Cup as one of the favourites.
In the South American group, Lionel Messi rescued Argentina with a hat-trick in Los Albiceleste's final game against Antonio Valencia's Ecuador to ensure that they - with Sergio Romero and Marcos Rojo in their ranks - qualified for a 12th successive time.
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