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You can get a 10-20% improvement altering the factory ECU. With direct injection, you can run some absurdly lean mixtures like the lean burn motors from the 80's did (think 16+ AFRs).
But they definitely would be less than ideal for emissions, so you won't find it from an OEM. Probably not the best for the catalytic converter either.
But yes, it can be done. We toyed with it for quite some time and found about a 15% improvement on pump and e85. While legalities prevent us from offering this, if you're using a DIY platform, you should be able to extract several more MPG with the right approach.
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