Contact the airline of your choice to inquire about purchasing standby tickets. Be aware that you will not be able to request flying on a particular day. Most airlines will issue you a range of dates around a four-day window.
Call the airline back one full day before you plan to depart to confirm the availability of your ticket.
Arrive at the airport two hours prior to your scheduled departure to check-in. Prepare to be bumped to another flight just in case. You are at the mercy of the airline at this point. Be prepared for overnight accommodations that may be necessary.
Do not check any bags unless you absolutely have to. With standby flights, it is possible that your luggage will end up on a different plane that arrives later than you do. Carry-on luggage will allow you to be more flexible.
Check-in at the gate to be double sure that you will be able to take that particular flight. Wait for your name to be called. Board the plan.