To change your working days and working times in Outlook, do the following:
1. On the File tab, click the Options button:
To change your work hours In the Start time and End time lists, click the start time and end time of your work day. This is primarily used for your free/busy time availability for meeting requests from other people. To set your work week Select the check boxes for the days that are a part of your work week. In Microsoft Outlook 2010 messaging and collaboration client, you can set your own calendar work days and working hours. By default in Outlook 2010, the work week is set from Monday through Friday with a work day extending from 8 A.M. The first day of the week in Calendar is Sunday. In your Outlook calendar, click the File tab, then OptionsCalendar. Under Work time, choose the Start time and End time, of your work day. Select the days of the week that you work, and clear the days that are not a part of your work week. Choose the First day of the week, that you start working.

2. In the Outlook Options dialog box, on the Calendar tab,under Work time:
- Modify Work hours
- Select workdays by checking of days
- Choose the First day of week and, if it needed, the First week of year.
Note: Unfortunately, Outlook does not allow custom shifts:
- Different times for different days of the week,
- The transition of working time in a day, when a work shift begins in the evening and ends in the morning. In this case, Outlook displays the message:
For example:
To verify the new settings, create a meeting request and click the Scheduling Assistant.It will show the updated work hours and display Monday as a non-working day for you. However,only Exchange users get the full benefits of work time settings because it allows other usersto check this information in the Scheduling Assistant.
Hours Calculator
See also this tip in French:Comment modifier les jours ouvrables dans le calendrier Outlook.