Ethanol both reduces the energy content of the fuel due to less liquid energy density, and also increases the effective octane. You can normally run an engine designed for 91 on 87 octane E10 or E15 blend no problem, as in you won't activate the adaptive timing system if you have one.
By the way, did the OP compare his mileage on the same hilly road? You actually can get better mileage over hilly terrain - when you're going uphill, your engine is running closer to peak efficiency due to the high power loading and more open throttle setting, while burning minimal fuel at idle on the downhill. The energy expended going uphill is recoverable I consistently get better mileage through the foothills than I do on flat land.
I live in the Catskills. Anywhere I go is a hilly drive.
I didn't take the same road on the return trip as I took on the trip out, but it was a road I do use regularly. Both are equally hilly, with about a 1,200 foot climb in the middle over the mountain, but almost the exact elevations on either end. They're also both very twisty, necessitating frequent speed reductions around the turns.
The only real difference between the two roads is that the one I used on the return trip is about three miles longer and goes through a couple of sleepy villages, so it adds maybe eight to ten minutes to the trip. But it also has a lower deer hazard, making it a better choice at dusk; and because of the villages, it has slightly better cell phone coverage and would make for a shorter walk to civilization if I were to get into an accident.
Basically, during the daylight hours in good weather, I take the shorter route to shave a few minutes off the time. From dusk to dawn or in bad weather I take the longer one for safety reasons. I doubt the car's engine cares very much which one I take. They're pretty much the same in terms of things an engine would care about.
I understand, agree with, and have also experienced the improved mileage on hilly roads in general. I also believe that if the higher octane helps at all MPG-wise, that's where it happens: going uphill. It prevents the timing from being retarded. That's about the only way higher octane in itself contributes to better MPG. But because that's a big part of my driving, I want to make a comparison with 91-octane corn-laced.
The other thing I have to consider economy-wise is that I get lower prices at Sunoco because of the deal they have with Price Chopper (a regional supermarket chain). At present I've accumulated a $0.57 / gallon discount on Sunoco gas based on routine grocery purchases at Price Chopper. (It goes back down to zero every time you fill up.) But I'd have to go to Mirabito for the ethanol-free, so I'd lose the Sunoco discount.
If I do decide to switch to ethanol-free all the time, I'll just have my dad get Price Chopper to issue me a loyalty card on his account so he gets the Sunoco discounts on my grocery purchases. Hey, someone may as well get them, and it may as well be dad.
Rich