Well, the probability of rolling a 5 would be 1/6, the probability of not rolling a 5 would be 4/6 or 2/3.
Since the problem uses or, the question is asking for the probability of one or the other occurring, in other words the probability is more that if it were to simply be one event. Thus we add the probabilities together.
1/6 + 4/6 = 5/6.