Question:

Is it Possible to add further picklist values to the Start Time (Start_time_vod__c) field on the Time Off Territory object in CRM?

Answer:

Yes, it is possible to add them. The new values are visible in the My Schedule. In order to configure this, the new values must be added to the Field Dependencies list for the Time_vod__c field.

Related Documentation:

CRM Help Documentation: Creating Time Off Territory in My Schedule