Cinque terre is in Liguria. You can spend a night in Lucca and drive to cinque terre from there or better in La Spezia that is the gateway to the area. The best way to visit the 5 little villages is by the local train from La Spezia, Alternately a great way to tour the Cinque Terre is by boat from La Spezia. The boat does not take reservation but it runs pretty often. The area can get really busy in peak season (May to Sep), it is better to visit it off season. The most famous, and most photographed, town of the Cinque Terre are Manarola and Vernazza, but all of them have same unique characteristic that make them worth a visit.