Yes, create a recurring appointment with the time "out of office" for your
non-work hours.

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Milly Staples [MVP - Outlook]
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After furious head scratching, blissrt asked:
| I set up my work week 7-3:30, yet when someone schedules a new
| meeting my time shows available beyond those hours. Consequently,
| they schedule meetings "after hours" unknowingly. Can I show my
| non-Work Week hours as "out of office"?