It'll activate the DLC's.But I suggest you to wait for a better discount.
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I did this a short while back. Had the base game, bought the UE for the DLCs. Works fine.
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I bought Fallout NV a long time ago on Steam, but I just found this, which is cheaper than buying individual DLCs, will I be able to activate the game with all the DLCs on Steam or it'll say I already own Fallout New Vegas?
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