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The tank is technically a 9.1L tank, so it's not quite 2.5 gallons- just barely over 2.4 gallons. I've gotten 9L in my tank before, but it did require "topping off" with the fuel pump, but there still seemed to be room to spare (sensor ohms was at 55ohm, I think completely full is ~0Ω). According to the KOMBI module, the gas station's pump shuts off at about 8.7L, so you don't have to squeeze too much more to get the full capacity.
I always buy Ethanol Free, either 91 octane or 88 octane depending on which station I get it at.
 
I don't know about the i3 for sure, but most BMW's are programmed to never actually use all of the fuel in the tank. A couple of reasons, one, is there is usually some crud in the bottom and even with the filter, it's not a great idea to try to suck it all up. Two, the pump is lubricated by the fuel...air isn't a good lubricant for it. Three, fuel injected engines don't really like air in the lines. So, the actual fuel tank size and what's usable may not be the same.
 
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