In the Python spirit of beautiful is better than ugly
Code golf method, using slice and unpacking (not sure if this was valid 4 years ago, but it is in python 2.7 + 3.3)
b,=a[4:5] or ['sss']
Nicer than a wrapper function or try-catch IMHO, but intimidating for beginners. Personally I find tuple unpacking to be way sexier than list[#]
using slicing without unpacking:
b = a[4] if a[4:] else 'sss'
or, if you have to do this often, and don't mind making a dictionary
d = dict(enumerate(a))
b=d.get(4,'sss')