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If you're talking about shotgun ammo early in the game, and I assume that you're early in the game, you mostly have to find it. Sometimes you find some in all sorts of containers around the Commonwealth. You can also buy ammo from Trashcan Carla when she shows up early in the game, also there's Trudy at the Drumlin Diner down the road southeast of Sanctuary Hills, past Concord.
As you move around the Commonwealth you'll just find ammo, and you'll find merchants who will sell it to you. Early in the game you may have trouble finding "caps" which are the currency in the game so guying ammo may be difficult. So looking around, and searching the bodies of anyone or anything you kill is your best bet for finding the ammo you need. Good luck!