I am using Office Home & Business 2013 outlook as an POP account for send/receive emails.
Seems you are using an non-English account in Outlook 2013, thus adding it through OWA might not be applicable for you.
That depends on your organization and the software and its versions that are in use. On the Exchange side, it is actually an Active Directory feature which is exposed via Exchange and intended as a corporate feature.
An alternative would be for your recipient to set a picture for your Contact item in their Contacts folder.
Regards,
Ethan Hua
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