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The process for sending photos via e-mail on export from Lightroom is not the most intuitive process to set up.
Scott Kelby has a tutorial for setting Lightroom up to pass the photos on to your e-mail client. Unfortunately for a lot of Windows users, the handoff from Lightroom to the e-mail client doesn't work so well.
Don't despair, as there is a solution. A member of the Lightroom user community, Steve Sutherland, coded a little application called MAPIMailer, whose sole function is to enable Lightroom to successfully hand off exported photos to your default e-mail client. It works on both XP and Vista, and its free. Thanks, Steve!