If you have set an email address in your User preferences, you can send email to other users and receive mail from them through the Wiktionary user interface. In order to do that, visit the user's User page, and follow the "Email this user" link. The email address you entered in your user preferences will appear as the "From" address of the mail, so the recipient will be able to reply.
Of course, users who have openly published their email addresses can be emailed directly. Emailing users through Wiktionary is a privacy feature that protects your email address from spam.