Its name comes from the fact that all of its members except APSA are from the Luxray evolutionary line. With the exception of Takoshi, Team Luxrio's members physically transform between their civilian and vigilante selves.
Although the team's actual formation was never shown, Flutterbolt, Grifray, Snowpelt, and Dustphin joined forces during a crime-wave that rose during the Eeveebot's war on Route 50. Flutterbolt and Grifray were already vigilantes at the time, while Snowpelt and Dustphin were recruited into the team. Akkinator joined after Kat gave the team official recognition as "volunteer defense forces".
The team moves around Route 50 quickly due to natural Shinx/Luxray agility and traveling on rooftops. Known enemies include the Thorned Rose Syndicate, which conspires against Route 50 and sells its secrets to various enemies.
Flutterbolt is a Luxray and the leader of the team. She is an all-around infantry fighter with excellent agility and strength, who relies on physical, feral attacks that are enhanced by electricity; she has, however, demonstrated abilities to manipulate electromagnetism. She possesses the Batman philosophy- that a criminal's fate is for the justice system to decide. Twiggy's physique as Flutterbolt are reinforced by her life in the forest, where she is one with the spirits of the wild.
- Flutterbolt originated as one of Twiggy's old avatars, a sleeping Luxray.
- It was partly named after Twiggy's real-life cat, Flutter, and partly named after Fluttershy from My Little Pony: Friendship is Magic.
Grifray is the most versatile member of the team. Although noticiably smaller than Flutterbolt, she makes up for her smaller size with a spitfire attitude and avian traits. With gold-feathered wings and talon-like claws, she can fly into areas that the other members cannot. There are implications that she was a vigilante before Team Luxrio.
- Grifray originated as one of Pokey's running gags, the "Grifray Invasion", in which the Grifrays were genetic abominations that Pokey had created, instead of her alternate form.
- In the first Luxrio story, Grifray was introduced as Grifrio; she later evolved into Grifray.
Snowpelt is a Shinx and the "sniper" of the team. Due to her smaller stature, she is faster but frailer than her teammates. As the only member not to transform when suiting up, Takoshi relies on hit-and-run or long-range techniques, in the hopes that she will move too fast for others to recognize her.
- Snowpelt is Takoshi's current Pokesona, and the only current Pokesona in the team.
- The name came from the name of her dA account, Snowpelt-IceClan.
Dustphin is another Shinx and the "speed" member of the team. She focuses more on delivering ferocious attacks, rather than on agility or movement. Like Grifray, Dustphin has a cheeky and vaguely spirited personality. She and Snowpelt may act in tandem.
- Dustphin was the name and appearance of FishPaste's original Pokesona.
- Sparkleaf originally feared it was not as well known as her current Pokesona, Aria.
Akkinator is a shiny Umbreon with an Absol horn. She is the team's stealth and maneuverability fighter. Originally a solo vigilante, Akkinator crossed paths with Team Luxrio while fighting the Thorned Rose Syndicate at Max's favorite bar. When she was arrested, Team Luxrio rescued her and several other vigilantes from a transport truck. Akkinator joined the team not long after. During missions, she acts as the ninja/spy of the team.
- Akkinator was APSA's first Pokesona.
- The name originated from Twiggy's nickname for APSA, "Akkie".
- Unlike Flutterbolt, Grifray, and Dustphin, her transformation does not occur in a capsule.
Sheep is not a vigilante. However, she is the technician and proxy for Team Luxrio, and has an Ops Booth located in the team's hideout. She maintains their transformation capsules and keeps track of their affairs, though she does not keep cameras or mics on them, as they are too likely to overload.
- She may have invented Team Luxrio's transformation machines.
- It is implied that she has a small crush on Whiskas.
- From the real-life perspective: The inspiration for Team Luxrio came from the fact that at one point, FishPaste, Twiggy, Pokey, and Takoshi all had some sort of Luxray or Shinx on their base.