Maximiliana was born in Nymphenburg Palace, the summer residence of the kings of Bavaria.

She was the last child of Maximilian I Joseph of Bavaria and his second wife, Caroline of Baden.

Her mother gave birth to eight children; her eldest brother, Maximilian, died in childhood.

Maximiliana's siblings included King Ludwig I, Caroline Augusta, Empress of Austria, Elisabeth, Queen consort of Prussia, Amalie, Queen consort of Saxony and Sophie, Archduchess of Austria; as well as Ludovika, Duchess in Bavaria, mother of Franz Josef's consort, Empress Elisabeth of Austria (Sissi).

In 1814, Maximiliana was immortalized by the painter Joseph Karl Stieler in an oil painting which appears embracing a lamb with her twin sisters Elisabeth and Amalie.