Octane rating is a measure of how resistant a fuel is to detonation or "pinking"; the higher the Octane rating, the more the fuel / air mixture can be compressed without detonation happening. To make this clear, octane rating is not a measure of the amount energy in the fuel, but is a measure of its resistance to detonation.
The advantage or higher octane fuels is that a higher compression ratio or supercharging ratio can be used, which then leads to a higher engine cycle efficiency, which in turn means more power output for a given fuel burn. However, to confuse things further, there are four principal ways to measure Octane rating, RON, MON, Lean Mixture and Rich Mixture ratings.
Road fuels tend to be measured on a RON scale, for which unleaded fuels tend to be 95 - 98 RON but are only 85 - 87 MON.
Avgas is measured on Lean Mixture (similar to MON) but also has a Rich Mixture Octane rating.
The Lean Mixture rating is 100 octane (15 octane higher than the comparable 85 MON for unleaded Mogas) but Avgas also has a Rich Mixture rating of 130 which allows higher supercharger boost pressures to be used without detonation occurring. This is particularly a problem when using high power settings at low altitude, for example during take off.