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Another option: [[User:Fedcas|Fedcas]] took the train from Firenze to Pratignone (eur 1,90, about 20 min), then it's a 5 min walk to the A1 highway (see the spot on the map, Pratignone is N-W from Florence, where A1 crosses A11). It's a big commercial area so there are lot of trucks during the working days.
Another great spot in this area is a big petrol station (also see map). Directions: from Pratignone station walk southward on Via di Pratignone. Turn left on Via degli Olmi, cross the bridge over the highway and turn right on Via di Limite. You will walk through a little tunnel and see a few houses on your right; after you´ve passed the last house, walk on the dirt to your right and step over a little fence to reach the highway. There´s a gap in the sound-wall through which you can get behind it. Now you´re on the highway exit-road and there´s a fence between you and the petrol station. Turn left and just walk a bit towards the highway to pass the fence.
Yet another option: take a bus from the train station (Santa Maria Novella) to the airport, where the A11 highway starts. (The best option is to take the bus that goes to the airport, as there are many busy intersecting highways in the area that are difficult to cross if you don't get dropped off in the right place.) There is a petrol station on via Vialle Alessandro Guidoni, near where the highway starts.