I had the chance to sit down with Shannon Braun, a Microsoft MVP, to talk about doing enterprise WPF development in the real world (download here). Shannon has been working for the past year on a large WPF project at a large customer here in the Twin Cities. During the podcast, we cover why WPF was used instead of WinForms, developer-designer integration, resources for getting started, and more. It's an informative 30 minutes and lays a good foundation for future podcasts around WPF.
You can check out Shannon's blog at www.sysknowlogy.com. You can also get some good WPF intro info at http://blogs.msdn.com/jfoscoding/articles/765135.aspx and a nice introduction at http://www.davidchappell.com/blog/2006/09/introducing-windows-presentation.