Tiu estas mia frato, kiu promenadas kun sia edzino = That is my brother who is walking with his wife.
If we use kaj we must say, Li kaj liaedzino iris Parizon = He and his wife went to Paris.
Since sia, being reflexive, can never form part of the subject of a sentence, we cannot say Li kaj sia edzino iris Parizon, because li and edzino are equally subjects of the same clause.
The above list will hopefully give you a few useful examples demonstrating the appropriate usage of "edzino" in a variety of sentences. We hope that you will now be able to make sentences using this word.