Make an Empty Website in Expression Web
In your toolbar, under File > New > Web Site

Pick Empty Web Site Save it in your My Documents >
My Web Sites folder with a name you choose. Note: Saving in
the My Web Sites folder ensures that EW's meta files will follow any
changes you make automatically. If you want to use a folder
outside of this, make sure in your General Site Settings that the box is
checked to use hidden meta files.
Go back up to the tool bar and click on the
white page with the down arrow and pick HTML.
This will give you an empty page.
Save it as index.html or default.html (check with your server as to which
one they use for home page direction. Make all your pages and fill
them with your content.
For making a
centered layout with Expression Web check out my tutorial.
If you wish to make a template for your entire website and use it to make your pages look at my Dynamic Template Tutorial
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