She was born in September 1788 in Srezojevci, Serbia, the daughter of wealthy farm owner[2] (of the vlasteličići class) Radoslav Vukomanović and first wife Marija Damjanović; however, the exact date is unknown.

In 1805 she married Miloš Obrenović, who on 6 November 1817 was elected the Prince of Serbia, making her Princess consort.

Miloš was frequently unfaithful to her; and on one occasion she came close to killing one of his mistresses in a violent physical attack.

Between 1829 and 1830 Prince Miloš commissioned a fine city mansion to be built in Belgrade for Ljubica and their children.

[3] Her husband's rule was harsh and autocratic; in June 1839, he was compelled to abdicate the throne in favour of their eldest son, Milan, who died shortly afterwards.