She held off competition from Jamie T's latest album, Kings and Queens, which reached number two.
The veteran singer said she would "never have dreamt" that the album would have charted again - let alone go to number one.
"But there you go, you never know what's round the corner do you?" she said.
Dame Vera revealed she was out in France celebrating with her daughter, who was "more excited" about the news than she was.
TOP FIVE UK SINGLES CHART
1. Pixie Lott (pictured) - Boys and Girls
2. David Guetta and Akon - Sexy Chick
3. Jay-Z, Rihanna and Kanye West - Run This Town
4. Mika - We Are Golden
5. Black Eyed Peas - I Gotta Feeling
Source: The Official Charts Company
Despite finding fame for a second time, Dame Vera insisted her singing days are "well behind her" and she has no plans to start recording again.
The album was originally released to coincide with the 70th anniversary of the declaration of war.
Four Beatles albums appear in the top 10, after the re-mastered full collection of their music hit shops during the week.
Sgt Pepper's Lonely Hearts Club Band reached the highest position at number five, followed by Abbey Road at six, Revolver in ninth place and Rubber Soul at 10.
Cribs' new album, Ignore The Ignorant, debuted at number eight.
In this week's singles chart, Mika, Mini Viva and Muse all had new singles out, which reached number four, seven and nine respectively.
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