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Hello, I have a weird question. If I have a electronic copy game on my GOG account, can I activate new(same) product from CD/DVD? Thank you. :)
You can have only 1 copy of a game on your account.

In case of The Witcher 3 you have the TW3 and it's 2 DLCs/expansion pass as well as the GOTY edition. The latter is also added to your account for free by GOG if you buy the base game and the 2 DLCs/expansion pass.