Well, it doesn't work if the aim of your question is bonding. But for polyatomics it's a measure of the ability of the element in a polyatomic to reduce, for eg.
NO3- + 4H+ + 3e- ---> NO + 2H2O E=+.96 (nitrogen reduction)
MnO4- + 8H+ + 5e- ---> Mn2+ + 4H2O E=+1.49 (Manganese reduction)