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Did some volunteering and at the sorting place it was very much sorting items in to grades, lowest stuff got sent off to Africa, the best stuff got sent to shops in affluent areas where they could charge a premium but it wasn't one of the national ones
greentricky-
Mrs GB did some volunteering at one many years ago. She was horrified at the fact that if one shop was overrun with stuff they'd just pass the bags off to one of the other charity shops nearby.
So if you donated a bunch of stuff to a charity you really cared about, say, Cancer Research, it could easily end up at the Minorly Wounded Axolotl Sanctuary a few doors down.
Greenbank
I used to think that charity shops in posh areas were likely to have nicer stock, but apparently the big chains like Cancer Research and Oxfam truck it around the country to even things up.