On 13 May 1817 Leopoldine was married to Dom Pedro per procuram (by proxy) in Vienna. At the ceremony the bridegroom was represented by Leopoldina’s uncle, Archduke Karl.
Embarkation took place in Livorno on 13 August 1817 among much celebration, and after an adventure-filled voyage lasting 81 days, Leopoldine arrived in Rio de Janeiro on 5 November and finally met her husband.
From a distance Pedro initially appeared to Leopoldine to be a perfect, well-educated gentleman, but the reality was very different. Dom Pedro was a year younger than Leopoldine and sadly rarely measured up to the descriptions given by the matchmakers. His temperament was impulsive and choleric, and his education but modest. Even spoken communication between the young married couple proved difficult, as Pedro spoke very little French and his Portuguese could only be described as vulgar.
In keeping with Portuguese tradition, at the age of eighteen Pedro Bragança not only had a string of amorous adventures behind him and was principally interested in horse racing and love affairs, but in 1817 (the year of his marriage to Leopoldine) he was living as if in wedlock with French dancer Naeomi Thierry, who was finally removed from the court by his father a month after Leopoldina's arrival in Rio de Janeiro.
The young married couple took up residence in six relatively small rooms in the Quinta Boa Vista in São Cristóvão. The inner courtyard and path to the stables were unpaved and the tropical rainfall quickly turned everything to mud. There were insects everywhere, including in their clothing, for the uniforms and court regalia made of velvet and plush rotted and turned mouldy in the heat and humidity.