Python - Return values from a function

Use a list comprehension. Change

for (item, value) in config.items(section):
    # the function returns at the end of the 1st iteration
    # hence you get only 1 tuple. 
    # You may also consider using a generator & 'yield'ing the tuples
    return (item, value) 

to

return [(item, value) for item, value in config.items(section)]

And concerning your test() function:

def test():
    aList = getItemsAvailable('test')
    print (aList)

Use a generator function:

def getItemsAvailable(section):
    for (item, value) in config.items(section):
        yield (item, value)

And get the items like this:

def test():
    for item, value in getItemsAvailable('test'):
        print (item, value)