The reunited girl group will put out a new retrospective collection titled Ten on November 26, which will feature a number of their most-popular hits.
The 18-track set will feature four new songs, including 'On The Metro', 'Beautiful 'Cause You Love Me' and 'Every Now And Then'.
The album will be preceded by new Children in Need single 'Something New' on November 18, with the group to perform the track live for the first time during the fundraiser on November 16.
Asked by Digital Spy if they feel they have anything left to achieve, Cheryl Cole said: "I think it's incredible that we get to share 10 years - it's a decade in music.
"If you'd asked us 10 years ago we'd never have thought we'd have achieved what we did."
Nicola Roberts continued: "To be back together for the fans and for them to enjoy that - that's all we want to achieve for now."
Cole added: "Touring is the best thing we do full stop. To say thank you to the fans is a special feeling."
[Girls Aloud are formed on Popstars: The Rivals back in 2002.]
Girls Aloud also announced plans to embark on a headline tour of the UK in support of the greatest hits disc in February and March 2013.
The jaunt will begin at Newcastle's Metro Radio Arena on February 21 and conclude at Liverpool's Echo Arena on March 20.
Tickets for the shows go on general sale from 9am on October 26. Fans who pre-order Ten between October 19 and 3pm on October 23 will gain access to an exclusive pre-sale.
The pre-sale will allow tickets to be purchased 48 hours before general release and be available from 9am on October 24.
The dates for Girls Aloud's UK arena tour is as follows:
Watch Girls Aloud's new video 'Something New' below:
Girls Aloud's career in pictures: