You may want to use a different structure altogether, but there are ways to do it in python 2.7.
d1 = OrderedDict([('a', '1'), ('b', '2')])
d2 = OrderedDict(c='3')
d2.update(d1)
d2 will then contain
>>> d2
OrderedDict([('c', '3'), ('a', '1'), ('b', '2')])
As mentioned by others, in python 3.2 you can use OrderedDict.move_to_end('c', last=False)
to move a given key after insertion.
Note: Take into consideration that the first option is slower for large datasets due to creation of a new OrderedDict and copying of old values.