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In most cases it should be fine. You may need to adjust cooking times & liquids to have everything come out right though.
If you are making tabouli, you can use substitute quinoa too.,
I think their flavors are different since barley comes as a whole and bulgur is a cracked wheat. I think couscous is a better alternative.
I would also highly recommend to try purchasing hard to find ingredients online. I just did a quick search on the internet and seems like this store carries bulgur. I wish you luck!