The 23-year-old started for the Three Lions for the first time in the friendly, partnering Danny Ings up front.
He put England in the lead at Wembley when Jack Grealish crossed in for him to head past Wayne Hennessey 26 minutes into the game.
Calvert-Lewin has had an incredible start to the season with the Toffees, having scored nine goals in six matches in all competitions for Carlo Ancelotti's team.
The most in-form striker in Europe's top five leagues, he took his tally up to 10 goals for club and country with his maiden goal for Gareth Southgate's side.
Calvert-Lewin is the first Everton player to find the net for England at Wembley in 35 years. England legend Gary Lineker was the last to do so, having netted a hat-trick in a World Cup qualifying match against Turkey in October 1985.
Calvert-Lewin has been tipped to continue his impressive form and labelled the "perfect number nine" by Everton academy director David Unsworth, while the player himself says he has been studying videos of AC Milan legend Filippo Inzaghi after comparisons from coach Ancelotti.
Meanwhile, Grealish's cross for his England team-mate saw him become the first Aston Villa player to register an assist for the national team since Stewart Downing set up Andy Carroll in the 1-1 draw with Ghana in March 2011.
Both Everton and Villa have had an excellent start to the domestic campaign, having won all of their games in the English top-flight so far.
The Goodison Park team are top of the table with four wins, while Villa are three points behind having played three matches - most recently a 7-2 thrashing of reigning champions Liverpool.