The Valentine's Day release, which sees Bruce Willis's John McClane head to Russia, earned more than £4.5 million in ticket sales to see off Disney animation Wreck-It Ralph.
This Is 40, the latest comedy from Judd Apatow, debuts at number three with £1.2 million ahead of musical Les Misérables. Beautiful Creatures, the supernatural teen romance starring Alice Englert, completes the top five with earnings of £1.1 million.
Elsewhere, children's animated movie Sammy's Great Escape is the only other new release to make the top ten, debuting at number eight with £519,049.
Outside the top 10 Keanu Reeves's documentary Side by Side pulled in £3,207 from seven locations, while Danny Dyer's Run for Your Wife earned just £602 from nine cinema venues.
> Danny Dyer's 'Run for Your Wife' flops with £602 at box office
The UK box office top ten in full:
1. (-) A Good Day to Die Hard - £4,551,115
2. (1) Wreck-It Ralph - £3,436,400
3. (-) This Is 40 - £1,229,352
4. (2) Les Misérables - £1,126,168
5. (-) Beautiful Creatures - £1,109,167
6. (3) I Give It a Year - £1,014,707
7. (4) Django Unchained - £685,389
8. (-) Sammy's Great Escape - £519,049
9. (7) Lincoln - £483,397
10. (5) Flight - £472,983
Watch Digital Spy's interview with Bruce Willis below: