An illustration competition named King of Combi (Japanese: キングオブコンビ) was advertised in the July 2021 issue of CoroCoro Comic, released on June 15, 2021, which invited people to portray their ideal Pokémon combination for an upcoming Pokémon TCG product. Copies of this issue included a postcard that had two blank TCG-style templates on one side for applicants to draw their entries, including the names of the two Pokémon and the combination name. Entrants were then required to mail their completed postcards to Shogakukan—those postmarked after July 14, 2021 would not be accepted. The winning combination, Pikachu and Eevee, was announced in the October 2021 issue of CoroCoro Comic, released on September 15, 2021. The entry would go on to form the basis of two Pokémon V cards illustrated professionally by You Iribi, which were revealed to be the focus of a special version of the Start Deck 100 in various media on December 15, 2021.
The overall winner of the King of Combi campaign received a copy of the deck upon release and an autographed print by manga artist Machito Gomi. Thirty runners-up also received a copy of the deck. 100,000 copies were also available to those who applied to purchase it. An insert with the February 2022 issue of CoroCoro Comic, released on January 15, 2022, included a QR code that linked to the application website as well as a serial code for entrants to input with their details. The application period was open between January 15 and February 14, 2022. Purchases were limited to one per person, and as the number of applicants exceeded 100,000, a lottery was held to determine purchase slots, and winners were notified in late February to return to the application website to complete their purchases before March 9, 2022.
The deck itself includes numerous reprints from the Sword & Shield Era and four exclusive cards: Pikachu V and Eevee V, which feature the CoroCoro Comic logo on their artwork, plus Wooloo and Dubwool, which have attacks that reference "CoroCoro". All of the cards are Mirror Holofoil. The deck also includes a Deck No. card like those from the Start Deck 100 that identifies the CoroCoro Comic Version as deck "000/100". Each deck comes packaged with a sheet of damage counters and status markers, a CoroCoro-themed 2-player playmat, a coin, and a player's guide.
Deck purchases were announced to be delivered in two waves in random assignment, and customers who completed their purchases were sent an email in mid March 2022 to confirm which delivery window they had been assigned to. The first wave was intended to be delivered in late March 2022, however as earlier shipments were done in plain envelopes without proper damage protection, many customers received damaged items and filed request for replacements, causing Shogakukan to pause the remaining shipments until April 2022, when the products were re-wrapped in proper packaging. Shogakukan promised to fulfill the replacement requests by May 2022. The second wave was initially announced to be delivered by late August 2022, but later moved to mid June 2022 due to manufacturing schedule adjustments.
In Taiwan and Hong Kong, the deck is released as a promotional product to celebrate the first anniversary of the official (Traditional Chinese) Pokémon TCG Channel, with the channel's logo printed on the top right corner of the package. It was only sold in Taiwan during the Ambassador Gym Tour, a series of events in which Ambassadors from the channel visit local Gyms and challenge players in 3×3 matches, and in Hong Kong during Regional League 2022-23 Hong Kong on November 13, 2022. The deck was never released in Thailand, and Thai copies of cards exclusive to the deck were distributed instead in promo card packs during a purchase event held between May 27 and June 30, 2022. The event required customers to purchase ฿300 worth of Pokémon Trading Card Game merchandise from B2S stores in order to receive a promo card pack.