She was born in Belgrade, Serbia, as Poleksija Ban, the daughter of Margarita Ban and Matija Ban, Serbian writer and diplomat.[2] The beginnings of her painting are linked to the drawing school of Jovan Deroko, and later to her husband Stevan Todorović.[3]
The Todorovićs traveled together to Florence and Rome, where they studied the works of Italian masters such as Raphael and Titian. They also worked jointly on numerous large historical and religious compositions.[1]
Poleksija Todorović taught art at the Higher Women School in Belgrade for 15 years. In 1907, she was among the founders of the Serbian Art Association (Srpsko umetničko udruženje).[2][4]
She died in 1939 and was survived by her youngest daughter Ljubica Todorović.[1]