Modern computer controlled vehicles should yeild better mpg with higher octane fuel. The computer cranks in more spark advance, which gives more performance...so you don't have to hold the hammer down so hard. The thing that worries me is how much of the octane comes from those corn squeezin's and how much is from just good gasoline. If your vehicle has "knock sensor" controlled spark advance, it should help to boost the octane. One of the best octane boosters is Amway's (I think it's Amyl Acetate...which is dirt cheap)...smells like bananas.
On our way home from VSC into NASTY headwinds (40-50mph), my ScanGauge II showed about 12mpg at 75mph (the speed limit in Utah and Idaho). I sure didn't blame it on the Sinclair, Texaco, or Chevron gas, or whatever we pumped in, tho there certainly can be some difference. On a really flat road with no wind, it should have been reading about 18-24 mpg at 75. It's a 2006 Toyota Tacoma 4x4, 6 speed manual, 4.0 V-6, DOHC, 24 valves, 236 hp, trailer towing gears, canopy on the back, no roof rack (but the rails are there).
The ScanGauge II
http://www.scangauge.com/ plugs into the computer port that the techie will plug into to scan for system faults. Mine sits on top of the steering column, and can tell you more than you'll ever want to know (for most folks). I have mine set to read MPH, RPM, MPG and H2O temp in F., but it can also tell me the spark advance and lots more. With just a little effort, it can teach you to get better MPG. Less RPM is key, coasting is good, etc. My brother got this thing for me for my birthday...trying to get ol' leadfoot to slow down, I guess. It came from Amazon, but you can buy them on eBuy and JC Whitney, even. Neat toy, and useful, to boot. Recommended!

Steve