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Go to Page Layout and select Print Titles.
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Check Row and column headings under Print Options and select OK.
Printing titles or row headers isn't currently possible in Excel for the web. You can, however, print titles or row headers in the Excel desktop app.
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To open the desktop app, at the top of the ribbon, select Editing > Open in Desktop App.
Don't have the Excel desktop app? Try or buy Microsoft 365.