Smith takes up the newly created post in February and will report to brand marketing director Jeremy Dale.
Smith has been at the high-street bank for several years and was instrumental in the merger of the Lloyds and TSB brands under then-marketing director Ford Ennals.
It is understood Smith's initial task will be to reinvigorate the brand's sense of passion within Orange, before taking a more hands-on role liaising with recently appointed ad agency Mother.
Her selection is the first major appointment by Dale, who joined last August after a stint as marketing chief at ITV Digital. Dale appointed Mother to Orange's £43m ad account following the most hotly contested pitch of 2002.
The company has been running a heavyweight debut campaign by Mother called 'Muck about', showing people in a series of humorous situations to promote its free picture messaging offer.