The obvious touristy thing to do would be Firenze - Siena - (Montepulciano if you like wine -) Pisa - Lucca (- Pistola -) Firenze. These are actually very pretty places (Firenze is worth spending a day or two alone). If you then plan your way between these accordingly and stay off the motorways, you can get a pretty nice ride and pretty scenery in as well.
If you have time towards the end of the trip, head north from Lucca towards Il Ciocco and the national park before looping back to Firenze. Nice scenery and nice riding there. If you still have time and cash leftover there, Il Ciocco has a good place to rent off-road bikes, they do tours and lessons as well, all on brand spanking new KTM 450 and 550's
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