You can create a dictionary using a dictionary comprehension as below
df = pd.DataFrame({'Type' : ['Pokemon', 'Pokemon', 'Bird', 'Pokemon', 'Bird', 'Pokemon', 'Pokemon', 'Bird'],'Name' : ['Jerry', 'Jerry', 'Flappy Bird', 'Mudkip','Pigeon', 'Mudkip', 'Jerry', 'Pigeon']})
f = df.groupby(['Type','Name'])['Type'].agg({'Frequency':'count'})
f.sort('Frequency',ascending=False, inplace=True)
d = {k:list(f.ix[k].index) for k in f.index.levels[0]}
print(d)
# {'Bird': ['Pigeon', 'Flappy Bird'], 'Pokemon': ['Jerry', 'Mudkip']}
The dictionary comprehension will iterate through the outer index ('Bird', 'Pokemon') and then set the value as the inner index for your dictionary.
It is necessary to first sort your MultiIndex
by the Frequency
column to get the ordering you wish.