The MAC address you get might not be practical to use. If someone has multiple network adapters then they also have multiple MAC addresses. And it's not uncommon anymore that someone has two networks. (For example, bluetooth, regular cabled and WiFi would already be three.)
A MAC address is just for identification and it can be requested. The Address Resolution Protocol is created for this purpose. By arping you can get a MAC address. Unfortunately, this only works on local networks, not on the Internet. I think that by using IPv6, you might also have a few options. Although I think it would still be limited to just a local system.
Getting the MAC address of your visitor might be considered inappropriate and perhaps even criminal since a MAC address is generally used as an unique identifier. This information could be misused by hackers, especially when the hacker manages to gain physical access to the users network. It would allow him to impersonate the user. Your site might make some security specialists very unhappy...
At http://www.ipaddresslocation.org/find-mac-address.php there's a Java applet which they claim will work. It doesn't on my system with Google Chrome, though.