Pretty much as Sean says, and a couple of the other points up there are correct too.
The main benefit of a higher octane fuel is the reduction in combustion retardation. So less chance of ‘throwing a rod’.
It means the chance of combustion occurring at top dead centre is reduced.
Also most premium fuels contain more lubricating additives, which is obviously a bonus for more high performance/tuned engines.
There is the MPG benefit with some higher octane fuels (more V-power), but that is mainly because of the fuelsave additives over other factors.
V-Power and Momentum are also the only pure blend 99ron fuels used out there.
They are blended to 98Ron minimum, and octane boosted through additives, to hit the 99ron mark.
Other 97/98Ron fuels are normal PU10 blends, at a 95ron minimum (standard fuel), then octane boosted to hit the advertised ron number.
We used to blend a SU10 (super unleaded, 10ppm sulphur) fuel, and that was at a 97ron minimum. But that has been phased out now, with the introduction of more efficient octane boosting additives.
In my personal opinion, a pure blend 99ron fuel is the best option for a performance/modified engine, and if your a petrolhead that cares about your baby, she’s worth the extra £3 a tank. Also in my experience, using v-power, that £3 is all but offset, with the extra MPG you can get.