Yes, you can hire a car from National at Brasilia Airport (their address is Area Externa Do Aeroporto Inte).
National does not offer free car hire cancellations at their Brasilia locations. To learn more about National cancellation fees, click here to find a list of phone numbers under the Locations tab.
Consider National as they have 7 convenient locations in the city. Our user data shows that the most popular National location in Brasilia can be found at Area Externa Do Aeroporto Inte.