The Church would take the position that your brother, as a baptized Catholic, is required to marry in the Catholic form. Going by only the information you have provided, it sounds as if the Church would consider your brother’s marriage to be invalid due to lack of form. Therefore, a full-blown annulment would not be required. That said, there may be other circumstances that we don’t know about that would change this conclusion. Your best source of information would be your priest.
Final thought: Since your brother has had nothing to do with the Church since his baptism, which I’m assuming he can’t even remember, I suspect that he couldn’t care less about how the Church regards his marriage.