The romantic movie, starring Channing Tatum and Rachel McAdams, took almost $2 million in ticket sales, closely followed by new entry This Means War with $1,955,381.
Denzel Washington's Safe House falls down into third place, while the revamped 3D version of 1999 movie Star Wars: Episode I - The Phantom Menace drops into fourth spot.
New entry The Grey, which tells the story of an Alaskan oil-drilling team struggling to survive after a plane crash, took $785,722 in box office sales, followed by Josh Trank's sci-fi film Chronicle, which made $763,752.
Australia's two home-grown comedies - Rachael Taylor and Josh Lawson's Any Questions for Ben? and Xavier Samuel and Olivia Newton-John's A Few Best Men - both left the top ten chart for the first time this week since their releases.
The Australian box office top ten in full below (figures in Australian dollars):
1. (1) The Vow - $1,979,041
2. (-) This Means War - $1,955,381
3. (2) Safe House - $1,461,000
4. (3) Star Wars: Episode I - The Phantom Menace (3D) - $790,673
5. (-) The Grey - $785,722
6. (4) Chronicle - $763,752
7. (-) My Week with Marilyn - $499,683
8. (-) One for the Money - $455,202
9. (5) The Descendants - $440,995
10. (9) Hugo - $314,279
Watch Digital Spy's interview with The Vow stars Channing Tatum and Rachel McAdams below: