MSN Messenger 

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NOTE: In order to block someone who's already a buddy,
follow these steps:

  1. Choose Messenger from Web Home.
  2. Choose Address book.
  3. In the listing for the person you want to block,
    choose Change.
  4. Choose Instant message settings.
  5. Uncheck (friend) is your buddy.
  6. On the following page, choose Done.