Barcelona to Cinque Terre along the southern coast of France

Here are a few nice places along the way that are in line with your interests...
* Collioure - a beautiful beachside village where many artists lived and worked during the late 1800s-early 1900s. A little touristy but you'll be there early in the season!
* Narbonne - the cathedral is quite spectacular - it wasn't fully finished but what is there is impressive!
* Pezenas - a very nice, ancient "village circulade" that is right on your way. Winding stone streets, beautiful shops, restaurants and churches. Antique stores are what this town is known for. Excellent weekly market if you are there on a Saturday.
* Abbaye de Valmagne - gorgeous former abbey that has been turned into a winery. Giant casks in the old side chapels of the church - it is off the beaten tourist track and lovely!
* Tarn Gorge - white limestone gorges at the base of the Cevennes. Kayak and swim under the ancient Roman bridge. Drive from there up the narrow valley to St. Guillaume le Desert - it's an old pilgrimage town that is tucked into the hills. Quaint and beautiful.
* Stop off to see the flamingos and horses of the Camargue.
Hope this gives you a few ideas!

Cassis - for hiking, swimming, and boating in the Calenques, as well as wine tasting nearby (for drivers).