She has one older brother, Prince Amedeo (b. 1986), one younger brother, Joachim (b. 1991) and two younger sisters: Princess Luisa Maria (b. 1995) and Princess Laetitia Maria (b. 2003). Her godparents are her paternal uncle Archduke Gerhard of Austria-Este and her elder paternal aunt Archduchess Maria Beatrix of Austria-Este, Countess von und zu Arco-Zinneberg.
Until 1993, she resided in Basel, Switzerland, at which point her parents relocated to Belgium. She was educated at the Jesuit school College Sint Jan Berghmans in Brussels. She completed her secondary education at the St. John's International School in Waterloo, Belgium. She then went to London, like her brother Amedeo (educated at the London School of Economics and Political Science), but attended SOAS in London, where she studied Chinese. In 2007–2008, she spent time in China as part of her studies. She then enrolled at the Institut National des Langues et Civilisations Orientales in Paris in 2008, where she is still studying. The Princess is fluent in French, Dutch, and German, the three official languages of Belgium.
On 9 September 2005, Maria Laura, along with six other students, were riding home from St. John's International School in Waterloo when the bus collided into three cars and rolled over several times. All of the students managed to escape before the bus burst into flames. The princess was unharmed but was taken to the hospital for observation and released to her parents after a few hours.
Because she is so distantly in line for the throne, her mother has guarded the private lives of her and her siblings, therefore, she and her siblings have rarely made public appearances. She appeared in family photos, at the baptism of her younger sister Princess Laetitia Maria, the wedding of Archduchess Marie-Christine of Austria and Count Rodolphe of Limburg-Stirum and her mother's 50th birthday celebrations