They will join 4,000 competitors from all over the world at this year's event from July 7-12.
Multi-million seller Barbara Dickson, who recently celebrated 40 years in the music industry, will step on the stage on the Tuesday to begin the first of the festival's six concerts.
A sensational acting and singing career started for the Scottish artist during the early seventies, when she was cast in an award winning musical based on the Beatles.
Firm favourite Sir Willard White returns to the Eisteddfod for Thursday night's concert to explore the life and music of the late Paul Robeson, American musician, actor, and icon of equality and human rights.
The evening, entitled Robeson Re-Explored, sees Willard White perform with a group of versatile musicians and a string quartet, bringing spirituals, jazz, and folk music to the stage.
Blake and Natasha Marsh both perform on the Friday evening.
Blake won the Album of the Year Award at the Classical BRITs last year.
The voices of Stephen Bowman, Jules Knight, Dominic Tighe and Ollie Baines produce a mixture of classical and operatic quality with a contemporary twist.
The boys said: "We've been lucky enough to visit Wales with Katherine Jenkins on a few occasions during this last year, and we're really looking forward to exploring North Wales when we attend the prestigious and well-loved Llangollen International Musical Eisteddfod."
Brecon-born soprano Natasha Marsh glides seamlessly from being a recording artist to enchanting opera houses all around the world.
Both her debut album Amour and her second album Natasha Marsh put her firmly on the map as a celebrated international artist.
This year 007 also comes to Llangollen when Carl Davis directs the music of James Bond with the Welsh National Opera Orchestra, Mary Carewe and Simon Bowman.
Actress Honor Blackman, who played Pussy Galore in an early Bond film, will host the Sunday evening concert.
Musical director Mervyn Cousins said: "The eisteddfod is developing and evolving each year, and we have more and more to offer competitors, visitors, and the local community annually.
"Llangollen is a well-established festival, and for us as organisers, extending the activities on the field on Sunday, July 12 is a natural process.
Tickets for the Sunday evening finale will include the Licensed to Thrill Music of Bond concert, as well as the day's events, and also a bonus concert by world-renowned violinist Tasmin Little - plus a firework display to conclude the festival.
The whole event kicks off in style on the Wednesday with the Llangollen Peace Concert hosted by eisteddfod president Terry Waite.
The welcome ceremony begins the evening when competition representatives from all over the world walk to the stage, and join together in an array of colour and friendship.
Conducted by Brian Kay, former founder and member of the King's Singers, youngsters from 10 different countries will then sing in harmony.
Deputy First Minister for the National Assembly of Wales, Ieuan Wyn Jones AM, who will be attending the launch of the festival, said: "The International Eisteddfod symbolises how national identity and true internationalism walk hand in hand - it would be a dull world without the variety of cultures celebrated every summer at Llangollen."
For tickets and further information call 01978 862001 or visit
www.international-eisteddfod.co.uk
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