Joss Whedon's superhero blockbuster sold 34 times as many copies as the second highest entry, Batman: The Dark Knight Returns - Part 1, across all disc formats.
The Avengers's success helped Marvel Studios' precursor films climb into the upper reaches of the chart, with Thor in eighth and Captain America: The First Avenger, The Incredible Hulk and the two Iron Man movies breaking the top 25.
Blu-ray format sales accounted for 72% of The Avengers's total unit sales, a record figure for a movie simultaneously released on DVD. The more costly 3D Blu-ray combo pack made up 23%, according to figures from Home Media Magazine.
Universal's Snow White and the Huntsman came in third place on the overall chart behind the Warner Bros Batman animation, with the Bond 50 collection of 22 James Bond films debuting in fourth.
The Avengers raked in more than $623 million at the US box office during its theatrical run.
Watch a clip from The Avengers below: