Step 1: Sign into Office 365 admin portal via https://portal.office.com
Step 2: Click on Admin from the left pane and navigate to Exchange admin center.
Step 3: Click on the Recipients and switch to Mailboxes tab.
Step 4: Double-click on the user to whom a manager must be assigned.
Step 5: Switch to Organization tab from the left pane.
Step 6: Under Manager field click Browse and select an account to be manager.
Step 7: Click Save.