To be able to send a mail you need a mail server (program) installed on one of the two computers, and a physical connection of course.
The easiest with Outlook is to use MS Exchange, but that is far from free, being from Microsoft, and it needs a professional IT-person to install and manage it. Same (more or less) for the equivalent program from Kerio. There might be open source programs available, but all of this seems much too 'heavy' for you.
But as soon as you don't talk about 'mail', but about 'file transfer' (using Windows Explorer to copy files from the one to the other or the other way around) it's all routine and standard available in Windows (from 95 up to Vista). All you need is the right cable to connect them and doing a little bit of setup.
USB-sticks are a marvellous way to transfer files also. But it can't be called 'mail'.
So please tell more about what you really want, and why you want it.
Is there a way to connect computers so they can mail each other without connection to internet, maybe using Outlook or any available (free is better) software?