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Born in Milan into a family of Jewish origins, Segre lived with her father Alberto and her paternal grandparents, Giuseppe Segre and Olga Loevvy. Her mother, Lucia Foligno, died when Liliana was not yet one year old.
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In 1938 Segre was expelled from her primary school after the promulgation of the Italian Racial Laws.
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On 10 December 1943, at the age of thirteen, together with her father, Segre tried to flee to Switzerland, but both were rejected by the Swiss authorities.
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In 1943, she was arrested with her family by fascists in the province of Varese at Selvetta di Viggiù.
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Segre was deported from platform 21 of the Milan Central railway station to the Auschwitz concentration camp.
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Her paternal grandparents were arrested in Inverigo, in the Province of Como, and deported after a few weeks to Auschwitz, where they were also killed on their arrival on 30 June.
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After some weeks spent there in terrible conditions, she was marched on to its satellite Malchow concentration camp.
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She was liberated by the Red Army. She was one of only 35 children who survived.
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After the Nazi Holocaust, Segre moved to the Marche region where she lived with her maternal grandparents, the only surviving members of her family.
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She met Alfredo Belli Paci, a Catholic political prisoner who had also survived the Nazi concentration camps.
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The two married in 1951 and had three children.
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She was among the witnesses of the documentary film Memoria, presented at the Berlin International Film Festival.
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On 27 November 2008, the University of Trieste awarded Segre with an honorary degree in Law.
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On 15 December 2010, the University of Verona awarded her with an honorary degree in Pedagogy.
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On 19 January 2018, the 80th anniversary of the Italian Racial Laws, the President of the Italian Republic, Sergio Mattarella appointed Segre as senator for life for outstanding patriotic merits in the social field.
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She proposed the establishment of a Parliamentary Control Commission on racism, antisemitism and incitement to hatred and violence, supported by Senator for life colleagues Renzo Piano and Elena Cattaneo.
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Due to numerous threats received on social media, she was assigned a bodyguard by the Prefect of Milan, Renato Saccone.
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Invited by David Sassoli for the International Holocaust Remembrance Day and the 75th anniversary of the liberation of Auschwitz, she spoke before the European Parliament, where she received an ovation by the full assembly.
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During the Sapienza University of Rome academic year inauguration, she was awarded a PhD honoris causa in European history.
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After 30 years of public witnesses about her life, she gave her last public speech in Rondine (Arezzo, Tuscany).
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On 26 October 2020, LUMSA University awarded her with an honorary degree in International relations.
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The University of Pisa awarded Segre with an honorary degree in peace and conflict studies.
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She presided over the Senate's section during which she proclaimed La Russa as new President of the Senate.