First, please verify that you are on SharePoint 2010 foundation domain such as mysharepointonline.com. This method only applies to SharePoint 2010 Foundation - not Enterprise level plans.
Go to Site Settings -> Site Permissions
Click Grant Permissions in the SharePoint 2010 Ribbon
Click the Create near the top of the form:
Enter your username and email to create the user and then grant permissions to the site.
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