The decision was taken after a meeting with some top executives of the Ghana Football Association (GFA) Normalisation Committee (NC).
The executive gave its approval and full backing to the plans of coach Appiah.
Ayew replaces Asamoah Gyan, his immediate past captain, who had led the Black Stars for a record seven years.
Gyan has been elevated to the position of "General Captain".
In view of the development, Kwadwo Asamoah, has been named deputy captain.
The president of the GFA-NC, Dr Kofi Amoah, who spoke to Joy News, has called on all stakeholders and citizens to support the transition whilst the Black Stars prepare to conquer Africa at AFCON 2019.
An announcement earlier that Gyan will not be captain of the team, forced him to resign from the team but after President Nana Akufo-Addo intervened, he made a u-turn and was named as part of the 30-member provisional squad on Wednesday afternoon.