Collecting up all characters in XCX will take you some time, and doing it as quickly as possible will require a studious focus on the game's many, many Affinity Quests.
In order to help you to collect 'em all (wrong franchise?), we've put together this quick-look character guide to where each of your newest and bestest pals can be found and added to your squad.
Xenoblade Chronicles X: Playable Character List - All 22 Unlockable Characters
Elma
Elma will join you from the start of the game.

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Lin
Lin joins you in Chapter 1.

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Irina
Irina joins you in Chapter 3.
Gwin
Complete Chapter 3 to unlock Gwin.
Doug
Complete Chapter 3 to unlock Doug.
Lao
Lao shows up during Chapter 4.

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L
Complete Chapter 4 to unlock L.

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H.B.
Complete the Affinity Mission "A New Rival" (Admin District, NLA) to unlock H.B.This mission will become available to you after Chapter 3, and once you have reached level 12.

Yelv
Get your level up to 15, complete Chapter 3, and then do the Affinity Mission "Meeting Yelv" to unlock Yelv. (Commercial District, NLA).

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Liesel
Becomes available for use after completing the Affinity Quest "New Skell on the Block".This mission recommends a level of 25, so it's doable fairly early on. Oh, and you'll get a new Skell, too!


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Frye
Compete the Affinity Quest "Bottoms Up". This quest requires you to complete Chapter 4 first, then you'll want to be around level 19 to breeze through. One other important point to note, this mission can only be accepted at night. The starting location is NLA's industrial district at the Repenta Diner.

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Boze
Head to the East Gate of the Admin District in NLA to accept the affinity mission "The Mad Monk". In order to start, you'll speak to Boze at the east gate and take on a request that leads into the mission.

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Mia
Complete the "Mamma Mia" affinity quest chain in order to add the fabulous Mia to your mix. Mia will give you the quest, and you can start it at the northwest of the Admin District in NLA , where you'll find her waiting on a platform.

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Murderess
Complete the "My Dream" Affinity Quest (Admin District, NLA, Hangar). Hit level 22, and complete chapter 5 to unlock access to this one!

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Phog
Complete Chapter 4, then head for the Water Purification Plant in the Residential District of NLA to complete the Foggy Dilemma quest.

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Hope
Complete the Hope Springs Eternal affinity quest (NLA, Residential District, Cathedral). You'll need to be level 21 and have completed the Marry Me! quest to accept this one.

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NeilNail

Complete "The Qlurian Archaeologist". You'll find this affinity quest at the BLADE Concourse to the right side of BLADE Tower in NLA. You'll need to be level 21, and have completed chapter 5 to unlock this mission!


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Nagi
To unlock Nagi, complete the affinity mission "Nagi Time" (Blade Barracks), which becomes available once you've completed Chapter 8.
Celica
Complete Chapter 9 and the "Manhunt" affinity mission.Once done, go to NLA's Industrial District to accept the "New In New LA" affinity mission. Simple! Sort of.

Ga Jiarg
Youll need to complete the Affinity Quest A Challenger Approaches to unlock Ga Jiarg. This quest requires a level of 42 (rec 46) and can be taken on from the BLADE Barracks in NLA.

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Alexa
Complete the Affinity Quest "Fitting In", which can be accepted from the Outfitters Hangar, NLA Industrial District. This mission requires level 46, completion of chapter 11, completion of BFFs side mission, and the Skell Flight Module.

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Alois Bernholt - The Hero
The final unlockable character in the game! AB will join your squad - alongside his rather exciting new Skell - during the events of Chapter 13 - Act 1. Easy!

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