No need for a car

There are three walks that start from Podere Sant'Angelo without having to use your car:

1. From Podere Sant'Angelo you can walk along 'strade bianche' (unmade roads) to the nearby village of Roccalbegna. This is a pleasant stroll that also takes you over a ford and can be a little steep in places. In summer there's a good chance that there's no water on the ford, otherwise use stepping stones in the two streams that come together here or take your shoes off!
   Duration: 70 minutes Difficulty: moderate (a little steep in places)
   
2. Rochette di Fazio is a beautiful hamlet down towards Saturnia that overlooks the Albegna valley, it's a pleasant walk to get there on foot from Podere Sant'Angelo. You walk down to the end of the 'strada biancha' and following the signed path cross over the stream (another ford) and then climb up an old mule trail to Rochette. There is a trattoria in Rochette, check the opening hours in advance as these vary according to the time of year. A shorter version of this walk is to drive down to the end of the road, park up and continue on foot from there.
   Duration: 5 hours round trip Difficulty: strenuous (the mule trail is quite steep)
   
3. It's pleasant to walk through the coppice woods to the castle at Triana. A third of this is on the 'strada biancha', you then cut into the woods and follow the signed path. Watch out for deer as you walk through the woods. Unfortunately, the castle is closed but you can enjoy great views along the Albegna valley to the Argentario peninsular and the sea. The return is by the same route (or, if you prefer you can walk along the road).
   Duration: 120 minutes (to castle) Difficulty: leisurely (a little steep in places)

Walks from Roccalbegna

There are several signed trails that start from Roccalbegna. A challenging, but rewarding, full day's walk is to take the trail that leads up to Monte Labro. This starts just outside the village and is well signposted. It's uphill all the way! There are a couple of shorter walks around the village and along the Albegna river.
Duration: Roccalbegna <-> Monte Labro: 5 hours Difficulty: moderate (all uphill to Monte Labro)

You can also walk around Monte Labro from the Parco Faunistico near Arcidosso. To do this park up by the entrance to the park and follow the trail on the map you'll get with your entry fee.
Duration: 3 hours Difficulty: moderate (some steep sections)

Pitigliano to Sovana and back

This is an interesting day's walk through the Etruscan landscape of the very south of Tuscany. The route takes you along part of a 'via cave' (a road cut out of the soft pumice rock by the Etruscans) and then along trails that take you past Etruscan remains and there are also some sections along roads (with next to no traffic). There are several 'trattorie' and a couple of bars in Sovana, before heading back to Pitigliano visit the 13th century cathedral.
Duration: 5 hours Difficulty: moderate (some short, steep sections along the 'vie cave')

Around Bagni Vignoni

The tiny village of Bagni Vignoni is famous for its hot springs and the large pool at its centre. Its location on the slopes of the Val d'Orcia makes it a great location for lots of great views over this iconic Tuscan landscape. There's an interesting circular three hour walk that takes you down to the river Orcia then back up to the hills above Bagni Vignoni from where you can look over to Pienza and Montalcino, you then return to Bagni Vignoni passing through the small hamlet of Vignoni.
Duration: 4 hours Difficulty: moderate (some steep sections along old mule tracks)

A circular walk starting and ending at La Foce

This walk starts from the car park of La Foce manor house. The house and its beautiful garden are worth visiting before setting out on this well signposted walk around the southern edge of the Val d'Orcia. For the first half of the walk you pass through oak woods before arriving at the hamlet of Castiglioncello del Trinoro with its five star 'albergo diffuso' (hotel with rooms spread throughout the hamlet). There are spectacular views across the valley. You walk down 'strade bianche', then along the side of the valley back to la Foce with amazing views across to Monte Amiata along the way. 
Duration: 4 hours Difficulty: moderate (there are a couple of steep sections)

Ask your host for more information about any of these walks.