I am trying to figure out the best way to address people on the outer envelop, since we don't have an inner envelop to use. Ie for a married female friend and her husband, the formal way is Mr. and Mrs. John Smith, But the invitation is actually to her and I would like to put her name on it, ie Mary and John Smith. Also for families would it be Mrs. Mary Smith and family?

Mr. John and Mrs. Mary Smith and family.

This dilemma is why there are two envelopes. You would still put Mr. and Mrs. John Smith on the envelope, regardless of who is your friend. Add and family if you are inviting the whole family. However, be advised that doing so can open you up to getting way more people invited to your wedding than you may have bargained for. My cousin did that and ONE response card came back with 36 people coming. You might want to reconsider the inner envelope as a way to control your guest list.

i don't know. But on mine they put Mr. and Mrs. John Smith