That would be... weird. From what I know and what my firewall previously has told me, Calibre only tries to connect to the Calibre web page on startup to see if there's an update available. I see absolutely no reason for it to try to connect to remote storage servers or even printers, unless my library would happen to reside on a remote server. Actually, I'd be rather shocked if it tried to connect to these things- I like my software to behave.
Edit: Why a connection to your home VPN would accelerate things, however, I don't understand.
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