Put an alias to Talkd in your Startup Folder, and launch it.
Put an alias to Talk somewhere useful, and launch it.
Set the Preferences via the Preferences menu, and click Save.
Choose Talk from the File menu and type in the recipients name, click Talk.
Choose Show Status from the File menu and watch the connection progress.
Wait until the person answers and a talk window appears. Your type into
one half of the window and they type into the other half.
Save the Talk menu with the Save Menu command.
You can quit Talk. Talkd will alert you when an incoming talk request arrives.
To respond just run Talk again.
If it doesn't work, try talking to yourself. If you don't have a DNS name for your Mac, you won't be able to connect to most unix implementations of talk, because they give up if they can't find your name. Talk is a braindead protocol (several actually), so sometimes it just won't work. Talk should be able to connect to most systems though, one notable exception being Apple's AU/X talk (ironic hey :-).