Protect was introduced in Generation II, it was in TM17. In Generation III, it was also in TM17.

Pokémon

Level-up

Pokémon Gold, Pokémon Silver and Pokémon Crystal

• Squirtle at Level 28
• Wartortle at Level 31
• Blastoise at Level 31
• Shellder at Level 25
• Cloyster at Level 1
• Krabby at Level 34
• Kingler at Level 38
• Omanyte at Level 37
• Omastar at Level 37
• Pineco at Level 1
• Forretress at Level 1

Pokémon Ruby, Pokémon Sapphire and Pokémon Emerald

• Squrtle at Level 28
• Wartortle at Level 31
• Blastoise at Level 31
• Shellder at Level 25
• Cloyster at Level 1
• Krabby at Level 41
• Kingler at Level 49
• Omanyte at Level 37
• Omastar at Level 37
• Pineco at Level 1
• Forretress at Level 1
• Mudkip at Level 37
• Marshtomp at Level 42
• Swampert at Level 46
• Dustox at Level 17
• Pelipper at Level 25
• Aron at Level 34
• Lairon at Level 37
• Aggron at Level 37
• Volbeat at Level 29
• Torkoal at Level 27
• Corphish at Level 23
• Crawdaunt at Level 23
• Anorith at Level 31
• Armaldo at Level 31
• Snorunt at Level 25
• Glalie at Level 25
• Shelgon at Level 30
• Salamence at Level 30
• Latios at Level 25

Pokémon FireRed and Pokémon LeafGreen

• Squrtle at Level 28
• Wartortle at Level 31
• Blastoise at Level 31
• Shellder at Level 29
• Cloyster at Level 1
• Krabby at Level 38
• Kingler at Level 42
• Omanyte at Level 37
• Omastar at Level 37
• Pineco at Level 1
• Forretress at Level 1
• Mudkip at Level 37
• Marshtomp at Level 42
• Swampert at Level 46
• Dustox at Level 17
• Pelipper at Level 25
• Aron at Level 34
• Lairon at Level 37
• Aggron at Level 37
• Volbeat at Level 29
• Torkoal at Level 27
• Corphish at Level 22
• Crawdaunt at Level 22
• Anorith at Level 31
• Armaldo at Level 31
• Snorunt at Level 25
• Glalie at Level 25
• Shelgon at Level 30
• Salamence at Level 30
• Latios at Level 25

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