The organisation aims to improve the performance of state-maintained secondary schools in specialist areas such as the arts, science, languages, music, sports and engineering.
It has brought Thame on board to increase the numbers of schools applying for specialist status.
She is charged with raising the profile of the organisation and creating a more integrated approach to marketing and PR.
Leading a 14-strong team, she will have responsibility for the organisation's press relations, marketing, publications and website, reporting to director of strategy and programme relations Ian Turner.
A priority will be ensuring there is greater awareness of the organisation among the public, particularly parents and teachers.
'Parents encourage schools to turn specialist, while we've increasingly found teachers don't know a lot about the programme,' said press officer Simon Horsborough, who will report to Thame.
The charity also wants to encourage failing schools to take part in its improvement scheme, which helps schools to support and advise each other.