if you want better MPG than be gentle on gas pedal and drive like a grandpa after defensive driving course
also make sure you have no mechanical issues with car like dragging brakes, worn out wheel bearings, etc also run some good fuel system cleaner (e.g. Techron concentrate) and keep all filters clean according to maintenance schedule to get the most out of it.
ECU will not let you do anything to A/F ratio, and honestly it's good, you would probably hurt it with any mods. toyota ECUs are really good in achieving correct A/F ratio accordingly to driving style. leave it alone.
check out
www.ecomodders.com for some minor (or major) mods for better MPG