Ace is on the execution platform, and the executioners raise their blades to end his life. In a desperate, primal scream to stop them, Luffy unleashes a massive wave of Supreme King Haki.
Monkey D. Luffy’s journey to becoming the Pirate King is marked by his mastery of Haki. Among its forms, (Haoshoku Haki)—also known as Supreme King Haki—is the rarest. Only one in a million people possess it.
3. Advanced Conqueror’s Haki: The "Supreme" Level (Wano Arc) which episode luffy use supreme haki
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While confronting the Flying Fish Riders, Duval’s massive pet bison, Motobaro, charges at Luffy. Subconsciously, Luffy glares at the beast, emitting a sudden pressure that terrifies the bison and causes it to faint. At this point, neither Luffy nor the crew understands what just happened. Episode 413: The Amazon Lily Arena
In one of the most satisfying demonstrations of his growth, Luffy walks past his crew mates on the Gyoncorde Plaza and knocks out 50,000 of Hordy Jones’s New Fish-Man Pirates in a single split second. Luffy’s journey to becoming the Pirate King is
[Ep. 518] Return to Sabaody (Fake Straw Hats) │ [Ep. 554] Fish-Man Island (50,000 Foes) │ [Ep. 716] Dressrosa Clash (Don Chinjao) │ [Ep. 723] The Doflamingo Spark Collision Episode 518: The Sabaody Reunion
If you are looking for the exact episode numbers where Luffy unleashes this legendary willpower, here are the most significant milestones in the anime:
Luffy used conquerors haki and man wtf (1st watch notes) : r/OnePiece