Piccioni was born on 14 July 1892 in Poggio Bustone (Province of Rieti, Umbria) and graduated in Law at the Sapienza University of Rome. He participated in the First World War, first as an officer of the Bersaglieri, then as a vehicle instructor.
After the War Piccioni moved to Turin, where he married, and joined the Italian People's Party (PPI). He became secretary of the Turin section of PPI and member of its National Council.
With the advent of fascism in power, in 1926, after the forced dissolution of the PPI, he moved to Pistoia, where he resumed practicing as a lawyer and became a widower. In 1943 he was a member of the National Liberation Committee of Tuscany.

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