You can verify your contact's cryptographic identity by confirming their Peerio ID#, preferably in person or over the phone.
You can find your own and your contacts' Peerio ID# by going to the Contacts tab and selecting a user's avatar.
Although Peerio will notify you if your contact's Peerio ID# ever changes (indicating a possible threat), it is a good security practice to verify your contact's Peerio ID# when communicating with them for the first time, and when sharing sensitive information.
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