No, Zoro is voiced by Gabriel Basurto and Bykuya is actually Christian Strempler. And Aloof Older Brother's aren't new to Alfredo, his most famous role was Sesshoumaru from InuYasha. ZORO is the role where he plays against type. And he nailed the role — but sadly the One Piece dub is VERY hated among Latin American fans for being based on the 4kids version of the show. Which is sad considering that, performance wise, it's actually pretty good.
Portuguese theatre actor, dancer, etc. Henrique Feist has had this at least twice: First, his most famous dub work would be in Dragon Ball, as Goku (as a plus, he voices him both as a kid and a grown-up). Not surprising, since most actors at that time (and some now) originated in such backgrounds. What's more surprising is his role in The Prince of Egypt, as Rameses.
George occasionally brought this up in his stand-up, including one of his HBO specials, when talking about the problems with kids these days. "This is Mr. Conductor talking! I know what I'm talking about!"
Ringo Starr later had played the same role. Imagine children's surprise upon discovering the Beatles and seeing Mr. Conductor with a band singing about drugs.