This was the first Pokémon TCG expansion available exclusively online. Japanese visitors to Pokémon Center Online could purchase 'packs' of ten cards and have their cards sent to them. After their purchase, users had the opportunity to view which cards they had bought online. The cards were packaged in clear plastic with a barcoded cover card featuring the set logo as opposed to traditional boosters.
Pokémon Web contained reprints of cards featured in Base Set, Jungle, Fossil and Team Rocket, along with several promotional cards. The cards were on the e-series card design, which likely added to their appeal. Rather than just producing complete reprints, MediaFactory brought old favorites into the new generation of the TCG. The set logo "Web" is in place of the "e" symbol as seen in future expansions. These cards featured a new division of Pokémon Powers into Poké-Powers and Poké-Bodies. Poké-Powers required activation to use, whereas Poké-Bodies were always active unless blocked by a specific card.
- The cards Dark Ivysaur and Dark Venusaur, featured in this set eventually made their English appearance as Best of Game promotional cards #6 and #7 respectively.
- The World Champions Pack would later become the second Japanese online-exclusive expansion in 2007. Advertised as a treat for Japanese players so they would not be at a disadvantage at Worlds 2007, it could be purchased in physical packs of fifteen.