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One day car travel from Siena to the Cinque Terre

In four weeks we will be driving in the Tuscany area and staying at an Agriturismo for a week. Have any of the savvy travelers ever had a one day driving experience from Siena to the Cinque Terre? La Spezia and Riomaggire...is driving to these two towns too ambitious in one day? Thoughts? Thank-you in advance.

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Not sure what you need to see in La Spezia, but to drive to Riomaggiore you need to drive through La Spezia.
I've driven from Florence to Riomaggiore many times. It's about 2 hours from Florence (and I know my way well). Considering that from Siena it's farther and you are unfamiliar with the roads, especially inside La Spezia, I would plan on 3 hours to get to Riomaggiore (with no intermediate stops). There is a parking structure in Riomaggiore after the barrier as you enter the village. Cars are not allowed any further into the town. You could also park the car in La Spezia at the station and take a train from there. More or less you are not going to save time either way.