I've gotten Amazon Prime deliveries on Saturday quite a lot, it's just never delivered by UPS or Fedex for that final stop. And Amazon does include Saturday in the two day guarantee, only Sunday is skipped.
UPS/Fedex & USPS don't work together out of altruism. It's a business arrangement, where UPS/Fedex does the long-haul part of the delivery and USPS does the last mile delivery. Both get paid, but less than either would for doing the entire thing. It works because the package is basically piggy-backing on shipping that would happen anyway. UPS/Fedex trucks/planes are heading between the distribution centers full of packages anyway, so adding a few more doesn't add to the costs much. USPS is going to be sending out people on the mail routes Monday through Saturday anyway, so a few more packages doesn't add to the costs. (Especially since UPS/Fedex takes it to the closest post office.)
It's a bit of a wash on package delivery time. If you live close to a distribution center (like I do), it usually adds a day to the delivery time. UPS will delivery to my local post office, often the same day it's shipped, and then I get to wait till the following morning before USPS brings it out. If you're further away, it may decrease the time. This isn't a major issue with Amazon, as they plan for the actual delivery date for each method and pick accordingly.
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