These products introduce Pokémon V-UNION to the TCG and, much like Pokémon LEGEND in the HeartGold & SoulSilver Series, require multiple cards to be played together. Pokémon V-UNION comprise four separate parts, each of which are included in one of the following sets:
- Greninja V-UNION Special Card Set (Japanese: スペシャルカードセット ゲッコウガV-UNION)
- Mewtwo V-UNION Special Card Set (Japanese: スペシャルカードセット ミュウツーV-UNION)
- Zacian V-UNION Special Card Set (Japanese: スペシャルカードセット ザシアンV-UNION)
Individual Pokémon V-UNION parts have different numbers and the assembly form a numbered master set. Each set also included three Skyscraping Perfection booster packs, three Blue Sky Stream booster packs, and a Supporter card depicting Professor Burnet that can aid players in discarding Pokémon V-UNION cards and bring them into play.
The sets were subsequently released in Taiwan and Hong Kong on August 27, 2021 and in South Korea on October 15, 2021. In Indonesia, the cards were available as S-P Promotional cards in V-UNION Promo Packs that were given to participants of Eevee Evolution Championship Battle events held between November 5 and December 30, 2021. They were similarly available as S-P Promotional cards in Thailand; V-UNION Packs were given away with purchases of a VMAX Climax booster box at participating stores between December 17 and 31, 2021. Each of these special packs contained all parts of one random Pokémon V-UNION and one Professor Burnet card.