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The earliest you can get this gear is when you reach White Orchard. This is one of the Treasure Hunts available in The Witcher 3. The Serpentine Gear is found during the side quest, Scavenger Hunt: Viper School Gear.
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For now, though, the Viper Steel Sword and Viper Silver Sword are more than enough to get your on your way. These are two swords can be found in White Orchard and are part of a larger set of armor which is only available through the Hearts of Stone DLC. The first set of unique swords you can unlock in The Witcher 3 is called the Serpentine Gear.
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