Good Rod in Safari Zone
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You can't catch a poliwag in Pokemon Sapphire. You have to trade from Pokemon Fire Red or Pokemon Leaf Green.
You can't catch wild Poliwhirl. You catch Poliwag though. Evolve your cute Poliwag into Poliwhirl by using a water stone. You can probably buy water stones in the department store in Celadon City.
You can not catch a Poliwag with an old rod. The only thing that you can catch with an old rod is a Magikarp. You need at least a good rod to catch a Poliwag. To get the good rod you will need to go to the house near the Warden House in Fuschia City. A fisherman will then give it to you. With it you will travel to Cerulean City and go to Bill's house and fish right by his house, you will then find a Poliwag.
poliwag is usually on the beach.
Poliwag is not catchable in Ruby, Saphire or Emerald.