He was born in a Slovene-speaking family in Trieste, Italy. His younger sister, Marija, became a translator and literary scholar. After World War II, the family moved from Yugoslavia to the Free Territory of Trieste. In 1966, he graduated from history at the University of Trieste and in 1971 at the University of Pisa. He continued his studies at the Diplomatic Academy in Vienna. In 1977, he obtained his PhD in Ljubljana under the supervision of historian Fran Zwitter. He initially researched the relations between Italy and the South Slavic peoples during the Risorgimento in mid 19th century. He continued with research on Russian history in the second half of the 19th century. Since the 1980s, he has been researching and publishing on the history of Yugoslavia, the Yugoslav wars and the history of the Slovenes in Italy.
He has taught history of Eastern Europe at the universities of Pisa, Trieste and Padova. He is currently head of the history department at the University of Primorska in Koper. In 1995, he became a member of the Slovenian Academy of Sciences and Arts.
He has also been active in public life, including party politics. In the 1990s, he was an active member of the Slovene Union, the centrist party of the Slovene minority in the Italian region of Friuli-Venezia Giulia. Since 2005, he has been an active member of the Liberal Democracy of Slovenia. In 2008, he unsuccessfully ran for the Slovenian Parliament in the district of Sežana. Pirjevec is both an Italian and Slovenian citizen. Besides Slovene and Italian, he is fluent in German, English, Serbo-Croatian, Russian and French languages. He is a member of the Honorary Board of the European Association of History Educators.
- Niccolò Tommaseo tra Italia e Slavia ("Niccolò Tommaseo between Italy and the Slavic World"). Venice: Marsilio, 1977.
- Storia della Russia del XIX secolo (1800-1917) ("History of Russia in the 19th Century (1800-1917)"). Padua: Francesco Vallardi, 1984.
- Tito, Stalin e l'Occidente ("Tito, Stalin and the West"). Trieste: Editoriale Stampa Triestina, 1985.
- Trieste, città di frontiera ("Trieste, a City on the Border). Trieste: Lint, 1989.
- Il Giorno di san Vito. Jugoslavia 1918-1992: storia di una tragedia ("St. Vitus Day. Yugoslavia 1918-1992: History of a Tragedy). Turin: Nuova Eri, 1993.
- Serbi, Croati, Sloveni : storia di tre nazioni ("Serbs, Croats, Slovenes: History of Three Nations"). Bologna: Il Mulino, 1995.
- L'altra resistenza: la guerra di liberazione a Trieste e nella Venezia Giulia ("The Other Resistance: the Liberation Fight in Trieste and the Julian March"), co-authored with Marta Verginella and Roberto Spazzali. Trieste: Qualestoria, 1995.
- Storia degli sloveni in Italia, 1866-1998 ("History of the Slovenes in Italy, 1866-1998). Co-authored with Milica Kacin Wohinz. Venice: Marsilio, 1998.
- Le guerre jugoslave, 1991-1999 ("The Yugoslav Wars"). Turin: Giulio Einaudi Editore, 2001.
- Foibe : una storia d'Italia ("Foibe: An Italian History). Turin: Giulio Einaudi Editore, 2009.
- Tržaški vozel. 1945-1980 ("The Trieste Knot. 1945-1980"). Trieste: Založništvo tržaškega tiska, 1985.
- Vojna in mir na Primorskem ("War and Peace in the Slovenian Littoral"), editor. Koper: University of Primorska, 2005.
- "Trst je naš!" Boj Slovencev za morje (1848-1954) ("'Trieste Is Ours!' The Slovene Struggle for the Access to the Sea (1848-1954)"). Ljubljana: Nova revija, 2007.
- Tito in tovariši ("Tito and the Comerades"). Ljubljana: Cankarjeva založba, 2011.
- Biography on the webpage of the Slovenian Academy of Sciences and Arts
- Biography on the webpage of the Faculty of Humanities of the University of Primorska
- Report on Pirjevec's campaign activities during the 2008 parliamentary elections on the webpage of the Liberal Democracy of Slovenia
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