As adviser for Team London, volunteering, charities and sponsorship, Wadley will work to build brand awareness of Team London, engage corporate partners and philanthropic foundations as well as developing relationships with the third sector.
She will also work with the Greater London Authority on identifying potential sponsors for wider programmes and projects.
Wadley will report to chief of staff and deputy mayor, policy and planning, Sir Edward Lister. She has declined to take the £95,000 a year salary for the first year of the job.
Previously Wadley was chair of the Arts Council, London and before editing the Evening Standard was deputy editor of the Daily Mail and The Daily Telegraph.
Mayor of London Boris Johnson said: 'Our army of volunteers have a huge passion for London and are a fantastic advert for us during the Games. Visitors are saying how friendly and welcoming our city is and I applaud the ambassadors for helping create such a wonderful atmosphere.
'I want to build on this amazing energy by expanding our Team London volunteers and I'm confident that Veronica Wadley will be instrumental in delivering more opportunities to everyone interested in getting involved.'
Outside of her career as a journalist, Wadley is a trustee of the Mayor of London’s Fund for Young Musicians and the Northern Ballet and advises the Greenhouse Schools Project charity.