I am trying to convert the dictionary
{0: {0: 173, 1: 342, 2: 666, 3: 506, 4: 94},
1: {0: 13, 1: 2171, 2: 1915, 3: 3075, 4: 630},
2: {0: 0, 1: 265, 2: 503
A Python-level loop is unavoidable here, so you can use a list comprehension:
res = np.array([list(item.values()) for item in d.values()])
# array([[ 173, 342, 666, 506, 94],
# [ 13, 2171, 1915, 3075, 630],
# [ 0, 265, 5036, 508, 11],
# [ 0, 3229, 2388, 3649, 193],
# [ 3, 151, 591, 1629, 410]])
As per @FHTMitchell's comment, this assumes your dictionary items (inner and outer) are ordered appropriately. Dictionaries are insertion ordered in 3.6 as a CPython implementation detail, and officially in 3.7+.
One way to define an order for inner and outer dictionaries is via operator.itemgetter:
getter = itemgetter(*range(5))
res = np.array([getter(item) for item in getter(d)])
Such a solution does not depend on the order of your input dictionary.