Dawn is staring at a Pokémon she finds cute. Brock and Ash watch what happens to that Pachirisu. Dawn adores it and wants to catch it, so she sends Piplup. Piplup goes to peck, but gets stopped and confused by Sweet Kiss. Dawn returns it and sends Buneary, who uses Dizzy Punch on it. Pachirisu retaliates with Spark, hitting her, so Buneary uses Ice Beam, but misses. Pachirisu electrocutes everyone, but is tired, so Dawn sends Piplup back. Piplup hits it with Bubblebeam and Dawn throws her Poké Ball, then catches the Pachirisu.
Jessie is happily skipping, though James and Meowth are not impressed. Jessie tells that she will compete in Floaroma Town contest and win the ribbon. James asks which Pokémon will she use, so Jessie plans to capture one first. In the night, Dawn is dreaming to win the Contest with Pachirisu. She wakes up and sees it sleeping, so goes back to dreaming. In the morning, Dawn has prepared herself for the new day, while Ash is excited to have his first badge. Dawn trains with Pachirisu and places her hand on its head, but gets electrocuted. Dawn is terrified to see her hair becoming a mess and calls Pachirisu back, but Pachirisu does not want to. Dawn sends Piplup and Buneary to take care of that problem.
They charge, though miss, as Pachirisu is very quick. They get tired after some time. Ash and Brock see this and Ash orders Pikachu to grab Pachirisu. Pikachu misses several times, as Pachirisu is too quick. Ash sends his other Pokémon, Aipom, Turtwig and Staravia. It is too quick and passes them, but after some time, Piplup and Buneary recover and corner it. However, Pachirisu escapes and is chased. They corner it once more and Pachirisu uses Discharge to damage them all, but then falls down. Dawn thinks Pachirisu is fine and shakes it, causing herself to be electrocuted.
Dawn makes her hair once more and wonders if Pachirisu does not like her. Dawn goes out of the tent and releases Pachirisu. Dawn tells it is free now to run wherever it wants, but Pachirisu seems to like her. Dawn runs away and Brock thinks she could eat to cheer herself up, but she does not want to. Dawn tells Ash and Brock she let Pachirisu out, as it caused a lot of trouble. Brock and Ash respond it is too early to release it. Pachirisu runs and comes to a spot and sleeps. Team Rocket see this and Jessie has the idea of capturing it. Dawn sees the clouds and thinks of Pachirisu. She comes back to Ash and Brock and is willing to capture it back. Ash and Brock tell they will help in this task.
Jessie throws her Poké Ball, but Pachirisu comes out and throws the Poké Ball at her face. The heroes see this and tell it is Dawn's. However, Dawn released it, but she is willing to get it back. To decide, they will see if Pachirisu wants Jessie or Dawn. Jessie takes the last food supplies. Pachirisu comes and electrocutes them, then eats the food. Dawn apologies to Pachirisu. Team Rocket try to take it, but Pachirisu is quick. So, they affect it's foot by throwing a goop, trapped. Dawn sends Piplup and Buneary, but the goop is thrown and they are affected. Dawn goes to protect Pachirisu, but gets also affected by the goop, along with Ash and Brock.
Dawn still protects it, but is defenseless. While Jessie and James are holding her, Meowth used a special potion that dissolve the goop out of Pachirisu's foot freeing it to catch it. Pachirisu runs away and Jessie wants it back. Pachirisu comes to Jessie. James and Meowth think they could get Pikachu, but Jessie tells them if they are more ambitious, their plans fail, so they fly away with Pachirisu. Jessie snuggles it, but Pachirisu uses Discharge and she, along with James and Meowth, get blasted off. Dawn is sad, but blames herself because of the choice Pachirisu made, but suddenly Pachirisu comes back. Dawn offers it to come with them and Pachirisu agrees, as it lets itself get captured.
- "Now you two stop gawking and turn around this instant!" - Dawn yelling at Ash and Brock after she gets shocked by Pachirisu.
- Dawn reads the title card.
- Dawn capturing Pachirisu is the first time since Ash received Pikachu in Pokémon - I Choose You! that a main character has obtained an Electric-type Pokémon.
- This is the first episode when a character releases a Pokémon and then recaptures it, not to be confused with the episode in which Ash trades his Butterfree for a Raticate and then trades back.
- The cold open format for this episode is a selection of two scenes from later in the episode, instead of a single scene.
- The instrumental version, the TV cut and the ballad version of By Your Side ~Hikari's Theme~ are used as background music.
- Professor Oak's lecture: Brock's Sudowoodo
- Pokémon senryū: しんかして もうなかないよ ウソッキー "You've evolved, so don't cry anymore, Usokkie."
- The next episode preview is narrated by Ash and J.
- The dub title is a reference to the phrase "Once bitten, twice shy".