Keep in mind I'm sharing advice or recommendations from a 2AZ-FE perspective, but our RAV4.2s still have more in common than otherwise.
1) My experience with unexplained worsening gas mileage has been attributed to slowly failing O2 sensors, on x3 different Toyota vehicles: x2 RAV4.2, x1 Tundra.
2) My alignment is readjusted every 3,000 miles . . . because it needs to be. That's how quickly they can come out of adjustment.
3) Tire pressures change with season. Pending no action by the owner/operator, they go softer in the winter, firmer in the summer.
4) On the subject of tire pressures, if your RAV doesn't have TPMS, be sure they aren't slowly going flat due to damage.
After the fuel system service this weekend, my mpg saw a major increase. But that was only for one day.
This is puzzling

A fuel system cleaner shouldn't be providing greater performance "during" the treatment. The combined chemical effects of PIB, PEA or PIBA should have the opposite effect on fuel burn: it's reducing the fuel's octane and introducing larger amounts of contaminated fuel. The benefit of a fuel system cleaner are realized "after" the treatment. This sounds like you got snake oil instead. What product was used for this?
Andeleon, I would recommend you replace the O2 sensors in your case.
The reduced mileage you're getting blows my best mileage out of the water. I have an 03 Rav 4 I get maybe 300km (~185mi) to a tank, 350 if I'm lucky.
I've ran about 5 bottles of fuel injector cleaner thru the system, both Lucas and Seafoam, with no luck. I changed out my PCV valve and hose and that helped a little bit bringing the mileage from 200-250km a tank to the aforementioned 300-350km. I have also plugged an exhaust leak after the resonator, changed out the bank 2 downstream o2 sensor, drained and filled engine oil and atf twice, checked for a stuck caliper, cleaned the throttle body, maf sensor, and idle air control valve, and checked valve lifter clearance. I have no engine codes and the fuel system enters closed loop after warming up. I've even busted out the stethoscope and listened to the injectors which sound perfectly fine.
The only issue left I can think of is the catalytic converter has a rattle at idle, but never under load, and that could possibly reduce airflow and cause slightly worse mileage. But even that shouldn't cause it to be anywhere near as bad as it is.
Sounds like you've done a good job covering the bases. I think your RAV4.2 is either running pig rich, or the engine is pulling a heavy load. I do 350 miles in the city and 450 miles highway with my 2AZ-FE on OME suspension and taller tires.
Things to look for if it's running rich: 1) How does the air filter look? 2) Is an injector stuck open? 3) Is the ECM commanding the injectors to run rich? (ECM error).
Things to be aware of if the engine is continually under load: 1) What size tires are you using? 2) What pressures do you run? 3) What aftermarket accessories have you installed?
I'm not the most knowledgable with the 1ZE-FE, so here's some documents you may find useful:
I might also start a thread discussing fuel additives, the chemical compositions, how often to use, where not to use, and the fact that non of them work as well as the manufacturers want you to believe.