An article was written here on this a long time ago. This is the updated version.
Windows Live Writer is arguably the best blogging app on the planet, so much so that even Mac users consider it the best over any similar app available for the OS X platform. Yes, it’s that good.
One of the annoyances with WLW however is that the default template, in a word, sucks. Hyperlinks are an annoying green and the default font used (Trebuchet MS or Calibri) is annoying to many.
The way to change this is to manually edit the CSS file for the default template.
Location of the default template CSS file
Whether on Windows XP, Vista or 7, the location currently is always the same – even if the new 2011 version:
[Host Drive]:\Program Files\Windows Live\Writer\Template
The file defaultstyle.css is the one you want to edit.
Editing the default template
I find the easiest way to go about this is to simply rename the file to defaultstyle.css-old, create a new defaultstyle.css and have it contain the following:
body,blockquote,table,td,tr,ul,li,ol,p {
font-family: sans-serif;
font-size: 10pt;
}
h3 {
font-size: 12pt;
}
.title {
font-family: sans-serif;
font-size: 14pt;
}
This will give you a basic editing template using Arial, the default sans-serif font in Windows. You can obviously specify any font you wish, so if you wanted to change to Georgia or Verdana, go ahead.
To switch to the default template at any time, use the keystroke CTRL+F11. You may have to do it twice for it to take effect.
If you want an exact copy of your blog’s template within WLW, copy over your CSS rules from your blog to defaultstyle.css – however be aware you must use full URLs for any image links or linked CSS files.
It’s also important to note that you should backup the defaultstyle.css you make, because upon any upgrade to Windows Live Writer the installer will overwrite with the default ugly default template again.

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Good information!
Additionally, Windows Live Writer doesn’t always detect the themes correctly, and its terribly irritating to come across this issue.
But you SHOULD still be able to use Windows Live Writer with those themes; you just need to make some manual adjustments. I’ve an article that are some options for Windows Live Writer users to try to help them with their theme issues.
http://www.lehsys.com/2010/02/windows-live-writer-creating-a-custom-template/
Someone should actually create a Windows Live Writer template creator, for when people don’t want to use a theme [but who would that be?].
Until next time,
LEHenryJr