Such live email addresses are very valuable to spammers. So this feature is susceptible to abuse by spammers providing the unsubscribe functionality, but only prioritizing the attempted unsubscribers higher in their mailing lists.
So built into their unsubscribe attempt, there needs to be a way to very strictly penalize those who pretend to allow unsubscribes while ignoring them to harvest more email addresses. Hence, they call it "unsubscribe and mark as spam" because any other email messages you receive from that sender will be marked as spam with extreme prejudice.