Hi @Alex-W
It is possible, but it's not a nice user experience. If you are wanting to display certain items when "All Employees" are in the combo box, you can use "in" in your formula to filter it.
The combo box returns a table as seen below. You can just use "All Employees" in ComboBox1.SelectedItems to apply logic triggered by "All Employees" being selected.

But if you really want to force it to "All Employees" when "All Employees" is selected, try this:
1) Set the "OnChange" formula to something like this:

If("All Employees" in ComboBox1.SelectedItems,
Set(varAllEmployees,true),
Set(varAllEmployees,false))
2) Set your "DefaultSelectedItems" formula to check for "All Employees" being selected:
If(varAllEmployees = true, {Value: "All Employees"}, Blank())

Now, if they choose "All Employees", it will reset the box back to your default "All Employees". Its kind of a bummer solution though, as its jarring to the user. Unselecting "All Employees" resets the box also, not great.
I would recommend just use "All Employees" in ComboBox1.SelectedItems to do whatever it is you're looking to accomplish with having only "All Employees" in the combo box