Not able to change email address . I am logged in as Administrator
If its server, you just have to go to the user management page and click on edit on one of the profile.
If its cloud, refer more information on this documentation
https://confluence.atlassian.com/cloudkb/changing-atlassian-account-email-addresses-969508513.html
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As mentioned by @Pramodh M , he has given solutions for two different environmen.
BTW:If the user account comes from an external directory, you may not be able to modify them.
https://confluence.atlassian.com/adminjiraserver085/configuring-user-directories-981154829.html
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