You should be able to but it won't be a matter of simply connecting the WD TV Live Hub to the computer with a LAN cable.
Depending on the functionality of your LAN ports, you may have to use a special patch or cross-over LAN cable connection. If neither of the LAN ports involved have auto sensing and correction for send/receive lines you will need the special cable.
Secondly, you will have to manually set up each device with a user specified IP address as your devices won't have access to a DHCP server to do that.
These may not be the only issues you would have to solve.
Gateway and 3 Portals, Samsung FP-T6374 TV, Panasonic DMR-E80, Denon AVR-3808, Sony CX777ES