The group will open the appeal night programme with their new single 'Gotta Be You', while Boyle will sing a track from her forthcoming album Someone To Watch Over Me.
The acts will be joined by JLS, Westlife and The Children in Need Collective, who will play this year's Children in Need single 'Teardrop'. The Collective includes Gary Barlow, Ed Sheeran, Ms Dynamite, Labrinth and Tulisa Contostavlos.
The event, which is broadcast live on BBC One on November 18, will also include appeal films from Kylie Minogue, Jessie J and Cheryl Cole.
The show will be presented by Sir Terry Wogan, Tess Daly, Fearne Cotton and Alesha Dixon.
Labrinth, who produced 'Teardrop', recently described working on the track to Digital Spy as "very healthy", adding: "It was a nice surprise to be asked by Gary to produce the song - everyone left their egos at the door."
Listen to One Direction's new single 'Gotta Be You' below: