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In theory, Chevron 94 should have more energy than 91 since there is no ethanol (though 91 Shell doesn't have ethanol), so Chevron 94 should yield better mileage. However, 94 is around 3 cents per litre more. So in the end, the $$ saving is probably minimal.
Driving habits probably play a bigger role for getting more mileage. You'd save more $$ driving around like a champagne colored Toyota Corolla driver.
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