Using dictionary comprehension, see Python Dictionary Comprehension:
from operator import itemgetter
dic = {'D': {('B', 2.0), ('E', 1.0), ('C', 2.0)},
'E': {('D', 1.0), ('B', 4.0), ('C', 3.0)},
'A': {('B', 1.0), ('C', 5.0)},
'B': {('A', 1.0), ('D', 2.0), ('E', 4.0)},
'C': {('E', 3.0), ('A', 5.0), ('D', 2.0)}}
# Simply extracting only the 1st element of the tuple from the key.
print {k:[alpha for alpha, num in v] for k,v in dic.items()}
print
# Extracting only the 1st element and sorting the tuples by its 2nd element, ascending.
print {k:[alpha for alpha, num in sorted(v, key=itemgetter(1))] for k,v in dic.items()}
print
# Extracting only the 1st element and sorting the tuples by its 2nd element, descending.
print {k:[alpha for alpha, num in sorted(v, key=itemgetter(1), reverse=True)] for k,v in dic.items()}
print
# Extracting only the 1st element and sorting by alphabetical order.
print {k:[alpha for alpha, num in sorted(v)] for k,v in dic.items()}
print
# Extracting only the 1st element and sorting by alphabetical order, lower()
print {k.lower():[alpha.lower() for alpha, num in sorted(v)] for k,v in dic.items()}
[out]:
{'A': ['C', 'B'], 'C': ['A', 'D', 'E'], 'B': ['A', 'E', 'D'], 'E': ['B', 'C', 'D'], 'D': ['B', 'E', 'C']}
{'A': ['B', 'C'], 'C': ['D', 'E', 'A'], 'B': ['A', 'D', 'E'], 'E': ['D', 'C', 'B'], 'D': ['E', 'B', 'C']}
{'A': ['C', 'B'], 'C': ['A', 'E', 'D'], 'B': ['E', 'D', 'A'], 'E': ['B', 'C', 'D'], 'D': ['B', 'C', 'E']}
{'A': ['B', 'C'], 'C': ['A', 'D', 'E'], 'B': ['A', 'D', 'E'], 'E': ['B', 'C', 'D'], 'D': ['B', 'C', 'E']}
{'a': ['b', 'c'], 'c': ['a', 'd', 'e'], 'b': ['a', 'd', 'e'], 'e': ['b', 'c', 'd'], 'd': ['b', 'c', 'e']}