From the “View” menu, select “Workspaces”. You’ll see all of the workspaces you’ve created. Select the workspaces you want to delete and click “Edit” -> “Delete Workspace”, or right-click and select “Delete Workspace”. If the workspace is “locked” to prevent changes, you’ll get an error message.
To unlock the workspace, click “Edit” (or right-click and click “Edit Workspace”) to pull up the workspace editor, uncheck the “locked” checkbox, and save your changes. You can delete the workspace once it’s unlocked.
In my experience, the workspace will continue to be shown in the drop-down list until you click on it, at which point p4v will figure out you’ve deleted it and remove it from the list.