>>> d = {'apple':9,'oranges':3,'grapes':22}
>>> v, k = max((v, k) for k, v in d.items())
>>> k
'grapes'
>>> v
22
Редактировать : Сортировать их:
>>> items = sorted(((v, k) for k, v in d.items()), reverse=True)
>>> items
[(22, 'grapes'), (9, 'apple'), (3, 'oranges')]