"Ele pediu um cão."
Translation:He asked for a dog.
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Pedir = ask as in request. Perguntar = ask as in inquire.
The rule for the verb perguntar is that you ask about something (direct object) to someone (indirect object). So "ele pergunta um cão" doesn't make sense, but you can say "ele pergunta a um cão" (he asks/inquires a dog).