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If you use Calibre there is a built-in web server which hosts your books (as long as your PC is on, of course.) This via the brower is my primary method to access my library with my Touch. Its enabled under 'sharing over the net'.
If you want that to connect to the world that depends more on if your ISP's terms of service, port routing, your local network configuration, IP address, etc. For example I have static IP and an ISP that allows me to run legal, non-commercial servers so all it takes for me is setting up my home router to pass through http and, viola!, my electronic bookcase on the world wide web.
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