One way to create styles in Dreamweaver is to start a new file (File > New) and choose "CSS" as the file type, then start typing the styles in text mode. Experienced CSS coders usually use this method. But there are other methods available for those who don't like to type things out in plain text.
Another way is to first create the HTML file, then click on the CSS icon in the upper right area of the screen.
This will open up a new side window and will allow you to create styles, link to style sheets, and edit existing styles.
The chainlink icon will cause a popup window to appear.

This will cause a popup window to appear.
class, tag, or id (or
pseudo-class).class attributes or the pound sign
( # ) for id attributes.<head> of
the document. 
Once you specify the type, name, and location of the style, you will see another popup window. From here you can specify styles by selecting your specifications from lists of options.

Some people like this method better than typing all of the styles. Others (like me) find it easier to type them, rather than hunt for all the properties in Dreamweaver's interface. One advantage to using the Dreamweaver interface is that it shows you what the options are for particular types of styles, and helps to give you ideas on how to apply the styles.

You can also edit the style properties directly in the side bar if you feel comfortable doing so. This method does not provide you with drop-down lists of options, but is faster for those who are familiar with the capabilities of CSS.

The following instructions assume that you have already created your style sheet and you just need to add the styles to the HTML page.
When applying styles to tags such as <p> or <body> or <h1>,
etc., you don't have to do anything to the HTML code
at all. As long as a style is declared in the CSS document,
the style will work.
When applying styles using the id attribute, you have to get
into the code view in Dreamweaver. You just go to the tag in the code and type id="whatever" in
the proper spot.
When applying styles using the class attribute, you have a choice.
You can either go to the code and type class="whatever" in
the proper spot, or you can follow the steps below:

If you want to apply a style to a portion of a sentence, or some other portion of a block level tag (e.g. if you want to highlight a phrase in a paragraph):
When you do this, Dreamweaver will automatically create a <span> tag
with the appropriate style.
Dreamweaver may be a powerful in many ways, but it is not powerful enough to display all of the styles correctly. When you start experimenting with advanced CSS, you'll notice that Dreamweaver can't handle it all. It would be nice if Dreamweaver could handle it, but it can't. You should preview the page in real browsers (Firefox, Internet Explorer, Safari, Opera, etc.) to see what the page actually looks like.
Dreamweaver allows you to preview pages by clicking on the F12 key. This will open the HTML file in your default browser. You can configure keyboard shortcuts for other browsers by setting your preferences in Edit > Preferences > Preview in Browser.
Avoid the following buttons in Dreamweaver's "Properties Bar", because they will either produce code that is not valid XHTML or add unnecessary items to your style sheet:
text-align instead
(e.g. text-align: center;) font-size instead
(e.g. font-size: 120%;) font-family instead
(e.g. font-family: Verdana, Arial, Helvetica, sans-serif;) color: red; or background-color:
red; etc.) 
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