No.
Getting involved with a married man is selfish on both the married man and whoever he cheats with parts. The married man is being selfish because instead of working on improving his marriage he is risking it all to be with someone else. Remember, honesty is the best policy. Also, the person he is getting involved with shares the fault. Nobody should ever cause the pain that affairs do. People need to stop thinking only of their selfish wants and remember that a married couple includes two, living beating hearts that are capable of feeling pain and embarrassment.
It is very wrong to get involved with any married person unless you are the person that he or she is married to.
It also depends on the relationship between the man and his wife, and your desires in the relationship.
If you desire a long term relationship then you may wish to evaluate his current actions (being married and having an outside relationship) and consider if that is acceptable to you, either as a long term girlfriend or as a possible future wife.
Since you believe that he willing to go outside this marriage, it is certainly possible that he would go outside his next marriage too.
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there is nothing wrong with talking to a married man as long as your not to flirty