Octane value just gives a measure of the chemical energy contained in fuel, so that fuels can be compared to one another relatively speaking.
This is not strictly true. (Although doesn't detract from most of the rest of this discussion). Calorific value gives a measure of the energy in fuels.
Octane rating is purely a measure of how resistant the fuel is to detonating, instead of burning when the flame is lit. It used to be calculated by comparing how a sample of fuel performed (detonation wise) v's a known sample of fuel with octane in it = the more octane required to match it, the higher the octane rating. (octane being 8 in the fuel series hexane heptane octane nonane decane etc, fuel being a mix of this and others, many others...).
Alcohol (ethanol) has an octane rating over 110, but a lower calorific value than most petroleum fuels, for example.