Go to your account's blacklist under Subscribers > Blacklist. You can add new entries either through manual input or by importing. Additionally, you can export all subscribers already on your blacklist.
To remove a subscriber from the blacklist, simply delete them from it.
Before sending a mailing, MAILINGWORK also checks against a global MAILINGWORK blacklist and some external blacklists, maintained by consumer protection organizations and advertising industry associations, to help avoid costly warnings. MAILINGWORK has no influence on these external blacklists.