It's possible. I'll have to check, but I was under the impression the Home version of XP was stipped of some of the networking features of Pro.
But it is possible to network them. What do you want to do with the networked PCs? How many PCs do you want to network together? Have both access and share the Internet connection? And will you want to just surf the Internet, play on-line games, etc? Will you want to share files/folders/printers between the PCs? what is your budget?
There are a number of ways to network them, depending on what your needs are. One of the simplest, basic ones is to put a second NIC in the XP box, connect the other PC NIC to that one, make sure they are on the same workgroup, and hard code an IP address range, such as 192.168.0.1 for the XP box, and 192.168.0.2 for the other one.
You can also purchase hubs/switches, and Internet gateways that will help make it easier to network.