>>> d = {2.9: [0.66], 3.3: [0.82, 0.48]}
First let's distribute the two keys of the dictionary into a list of tuples:
>>> ts = [(k, x) for k, l in d.items() for x in l]
>>> ts
[(3.3, 0.82), (3.3, 0.48), (2.9, 0.66)]
I'm using a two-level list comprehension, which is syntactic sugar for the equivalent nested loop.
Then you can transpose the list.
>>> result = zip(*ts)
>>> list(result)
[(3.3, 3.3, 2.9), (0.82, 0.48, 0.66)]
Or as a single expression, using a lazy generator expression instead of a list comprehension:
result = zip(*((k, x) for k, l in d.items() for x in l))