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This may be because you are trying to call a contact from the main address book on your iPhone or iPad, rather than from your Skype contact list, so make sure you are viewing your contacts within the Skype application.
You also cannot call or video call your Messenger contacts if they are not signed in to their Microsoft account using Skype.
If a contact from your Skype contact list doesn’t have a Skype account, they cannot participate in a video call. You may have added a new contact by manually typing in a new name and phone number in your Skype contact list, but if no Skype account is associated with that person, you can’t video call them.