"Encounters Trigger Chemical Reactions" (Japanese:
On the bus ride back to Karasuno, all of the players are sound asleep. Ukai takes the chance to thank Takeda for all that he has done to help the team; stating that if he hadn't been able to arrange to many practices matches and training camps, the team wouldn't have gotten the chance to becomes as strong as they are now and Karasuno's relationship with Nekoma was re-established.
In a dream, Daichi remembers when he, Sugawara, and Asahi first joined the volleyball club as first years. When Daichi reveals that he joined Karasuno after watching them at Nationals, the team captain becomes inspired to win nationals. When an advisor leaves the gym, Sugawara learns that the team doesn't have a proper coach. After one practice, the team captain, Hidemi Tashiro, admits that practices are now much harder than in middle school since there is no one helping them with things they need to do.
As a tournament is nearing, Daichi realizes that the Karasuno team has not had a single practice match. Asahi and Sugawara inform him that most of Karasuno's contacts with other schools have practically faded since Ikkei Ukai left. Second year Hiroki Kurokawa states that the other schools simply do not want to waste their time with them.
While Daichi was aware that Karasuno was no longer the champion team is once was, he had believed that the team would rise to glory once again as long as they continued to practice. One day, he is surprised to hear that the girls basketball team is needing the gym and learns this is because they were Karasuno's biggest chance to make it to Nationals, thus cutting the time the boys volleyball team would have in the gym.
With the team looking like it would not be moving forward, Daichi takes it upon himself to start staying for extra practices with Sugawara and Asahi joining him. Together, the three began looking into plans, plays, and other things that might help them and the team become stronger. Daichi was even able to recruit Kiyoko to be the team manager.
The day before the Interhigh, Tashiro declares that the volleyball team should try to make it to nationals when another players suggests they aim for a more 'realistic' goal as aiming too high would cause other to become discouraged. Despite some of the players uncertainty, Tashiro is still able to inspire them to reach the national stage.
Unfortunately, Karasuno would lose in the second round and the third years would retire from the team. When Tashiro is stepping down at the captain, he admits that the time the team started to unify happened too late and that opportunity will present itself to those who are prepared. Uncertain of if and when Karasuno would ever become strong again, Tashiro encourages the three first years to seize any chance they have to rise to the top. Shortly after the third years retired, Ikkei returned to the team.
Daichi awakens when he hears Kageyama yelling at Hinata for drooling. Upon entering the gym, Daichi reminds everyone that their goal is to win nationals. Though everyone is surprised at his declaration, Kageyama simply states that this is their obvious goal and is scolded by Tanaka and Hinata for ruining Daichi's moment.
Daichi clarifies that he previous stated that they should 'attend' nationals but now they should win. The rest of the team quickly agree with Ukai using their enthusiasm to start the meeting for their match against Shiratorizawa.
- Keishin Ukai
- Ittetsu Takeda
- Hisashi Kinoshita
- Asahi Azumane
- Yū Nishinoya
- Tobio Kageyama
- Tadashi Yamaguchi
- Kei Tsukishima
- Kōshi Sugawara
- Daichi Sawamura
- Hitoka Yachi
- Kiyoko Shimizu
- Lev Haiba (mentioned only)
- Keiji Akaashi (mentioned only)
- Haruki Komi (mentioned only)
- Kōtarō Bokuto (mentioned only)
- Kenma Kozume (mentioned only)
- Tetsurō Kuroo (mentioned only)
- Daiki Ogano (mentioned only)
- Masaki Gōra (mentioned only)
- Ikkei Ukai (flashback only)
- Shōyō Hinata
- Chikara Ennoshita
- Kazuhito Narita
- By Daichi, Sugawara, and Asahi’s first year, Coach Ukai had already left and a teacher advisor was in charge of the Karasuno High boys volleyball team instead. As a result, the team wasn't able to participate in practice matches.
- In the past, Karasuno Girls' Basketball Team was Karasuno's biggest chance at nationals.