The minister joined the couple together as man and wife.

my reply
The minister joined them together as man and wife.

husband or leave off as man and wife

To answer your question, it seems like you're asking whether you can use "husband" instead of "man" when describing the minister joining the couple together. Yes, you can definitely use "husband" as an alternative to "man" in this context. It would be grammatically correct to say, "The minister joined them together as husband and wife." This phrasing more specifically refers to the marriage relationship by using the term "husband" instead of the more general term "man." However, if you choose to leave off the phrase "as man and wife" altogether, the meaning of the sentence might be less clear.