The majority of settings for the Workflow extension are found in the Content - Workflow Plugin.
You can find these settings by going to the Plugin Manager, and clicking the the Content - Workflow plugin.
Settings are defined as follows:
Approval Notify Users: Users selected here will recieve email notifications of staged content.
Allow Users to Enter Notify Emails: When set to yes, this presents a text-entry field on the workflow screen that allows for the ad-hoc entry of one or more email addresses to be included on email notifications of staged content.
Can View Staged Versions: Specifies which users will be able to review and use staged content from the Versions window below the article.
Always Notify?: Hides the checkbox allowing the optional notification of staged content.
Always Notify On New?: When set to yes, emails Approval Notify Users when new content is created.
Unpublish New Articles?: When set to yes, will force new articles to be unpublished. Note that users with sufficient access can use Joomla's Article Manager to later publish that same content.
Unpublish Only From Usergroup: Works in tandem with "Unpublish New Articles" and forces unpublishing only from the selected user groups. Does not support custom Joomla user groups.
Stage All Changes? A global setting that will force all article changes into a staged state regardless of the workflow window settings or display.
Always Stage From Usergroup: Forces staging of articles from the selected user groups.
Display on Front End?: When set to yes, will also enable the Workflow button for front-end users. Otherwise displays as a disabled button.
Popup Window Width/Height: Allows for setting the dimensions of the Workflow popup window.
This is a quick demo on how Workflow is used.