С 2005 года по март 2018 года Амбросио встречаетсявстречалась с бизнесменом Джейми Мазуром<ref>[http://www.famoushookups.com/site/relationship_detail.php?name=Alessandra-Ambrosio&relid=4785&celebid=19/ Alessandra Ambrosio and Jamie Mazur | Married Divorced Children Ex | Famoushookups.com]</ref>. 24 августа 2008 года у пары родилась дочь Аня Луиза Амбросио-Мазур<ref>[http://www.actressarchives.com/news/alessandra-ambrosio-gives-birth-to-baby-girl/ Model Alessandra Ambrosio gave birth to her first child, a daughter named Anja Louise] {{webarchive|url=https://web.archive.org/web/20110519152222/http://www.actressarchives.com/news/alessandra-ambrosio-gives-birth-to-baby-girl |date=2011-05-19 }}</ref>, а 7 мая 2012 года — сын Ноа Феникс Амбросио-Мазур<ref>[http://omg.yahoo.com/news/supermodel-alessandra-ambrosio-pregnant-second-child-003409579.html/ Model Alessandra Ambrosio is pregnant with her second child] {{webarchive|url=https://web.archive.org/web/20120113164942/http://omg.yahoo.com/news/supermodel-alessandra-ambrosio-pregnant-second-child-003409579.html |date=2012-01-13 }}</ref><ref>{{cite web|url=http://www.dailymail.co.uk/tvshowbiz/article-2141029/Alessandra-Ambrosio-gives-birth-baby-boy.html|title='We couldn't be happier!': Victoria's Secret model Alessandra Ambrosio gives birth to baby boy Noah Phoenix|publisher=Daily Mail UK|lang=en|accessdate=2012-05-08|archiveurl=https://www.webcitation.org/68B8Fgm6g?url=http://www.dailymail.co.uk/tvshowbiz/article-2141029/Alessandra-Ambrosio-gives-birth-baby-boy.html|archivedate=2012-06-04}}</ref>.
С лета 2018 года встречается с основателем итальянского бренда «Alanui» Николо Одди.
