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Yes, Smashwords can distribute to Amazon, B&N, Sony, Kobo, and iTunes, which are the majors who have associated e-readers, and your books will also be available directly on their site to everyone around the world in multiple formats for people who can't shop at those other stores.
The one real drawback is that Smashwords' notorious automated "Meatgrinder" can sometimes produce poor formatting, so you might be better off formatting your e-book and uploading it to Amazon, iTunes, and possibly B&N yourself (you may not be able to do B&N directly if you are not a US resident) and letting Smashwords distribute to the other stores.
Also, I think you have to do a few extra things in order to make your book eligible for distribution to the other stores, but it seems to be fairly easy, judging from the amount of Smashwords stuff that shows up elsewhere.
Hope this helps, and welcome to MobileRead!
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