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The river originates on Monte Falterona^[3] in the Casentino area of the Apennines, and initially takes a southward curve. The river turns to the west near Arezzo passing through Florence, Empoli and Pisa,^[4] flowing into the Ligurian Sea^[5][6] at Marina di Pisa.^[7][8]

With a length of 241 kilometres (150 mi), it is the largest river in the region. It has many tributaries: Sieve at 60 kilometres (37 mi) long, Bisenzio at 49 kilometres (30 mi), Ombrone Pistoiese at 47 kilometres (29 mi), and the Era, Elsa, Pesa, and Pescia. The drainage basin amounts to more than 8,200 square kilometres (3,200 sq mi) and drains the waters of the following subbasins:

• The Casentino, in the province of Arezzo, formed by the upper course of the river until its confluence with the Maestro della Chiana channel.
• The Val di Chiana, a plain drained in the 18th century, which until then had been a marshy area tributary of the Tiber.
• The upper Valdarno, a long valley bordered on the east by the Pratomagno massif and on the west by the hills around Siena.
• The Sieve's basin, which flows into the Arno immediately before Florence.
• The middle Valdarno, with the plain including Florence, Sesto Fiorentino, Prato, and Pistoia.
• The lower Valdarno, with the valley of important tributaries such as the Pesa, Elsa, and Era and in which, after Pontedera, the Arno flows into the Ligurian Sea. The river has a very variable discharge, ranging from about 6 cubic metres per second (210 cu ft/s) to more than 2,000 cubic metres per second (71,000 cu ft/s). The mouth of the river was once near Pisa but is now several kilometres westwards.