I don't think you can block it, it's a security feature - should only need accepting once.
You can do a couple of things, you can search for users or get a specific user by handle like this:
Sub test()
Dim s As SKYPE4COMLib.Skype
Dim user As SKYPE4COMLib.user
Dim users As SKYPE4COMLib.UserCollection
Set s = New Skype
Set users = s.SearchForUsers("Dave")
For Each user In users
Debug.Print user.Handle, user.FullName, user.PhoneHome
Next user
Set user = s.user("dave123")
Debug.Print user.Handle, user.FullName, user.PhoneHome
End Sub
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