Check out this article to know which free Sync Pairs are the best in Pokemon Masters. This includes their stats and when you unlock them.
Table of Contents
Recommended Free Sync Pairs
Rosa & Snivy

Unlocked In | Chapter 1 |
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Extremely versatile with both support and offensive skills, Rosa & Snivy can easily fit any team composition. One of their moves also shortens the cooldown of the team's moves!
Check Out Rosa & Snivy HereErica & Vileplume

Unlocked In | Chapter 5 |
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Erica & Vileplume's strength lies on how their skills worth exceedingly well together. With a high stun rate and a skill that gives additional damage against stunned enemies, they can stun lock & down enemies.
Check Out Erika & Vileplume HereClair & Kingdra

Unlocked In | Chapter 13 |
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Althrough Clair & Kingdra will take longer to unlock, their strength is worth the wait. Their Meteor Move is powerful and can easily take down enemy health.
Check Out Clair & Kingdra HereHau & Raichu

Unlocked In | Chapter 11 |
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Hau & Raichu's speed makes it hard for enemies to land hits on them. If an enemy does hit, there's a chance for them to get stunned thanks to the paralysis passive.
Check Out Hau & Raichu HereFlint & Infernape

Unlocked In | Chapter 12 |
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A purely offensive pair, Flint & Infernape has a set of moves that benefits from their skill that raises their attack and speed.
Check Out Flint & Infernape HereHow to Unlock Free Sync Pairs
Complete Story Chapters for the First Time

Each story chapter will reward you with at least 1 Pair Sync as long as you complete all of the quests inside and defeat the Chapter Boss.
Check Out the Battle System Guide HereSet Pair Sync Reward per Chapter

You won't be able to choose which Pair Sync to get after each Chapter since they're tied to the story. You'll have to progress through the story to get them all!