Born in the Montenegrin village of Čevo, Milena was a daughter of VojvodaPetar Vukotić and Jelena Vojvodić born in the village of Viš-Danilovgrad Montenegro. Her father was one of the greatest landowners in Montenegro and a close friend of Vojvoda Mirko Petrović-Njegoš with whom he had fought in the wars of the 1850s. The two friends decided to consolidate their alliance with the union of their children. In 1853, Milena, age only six, was betrothed to Mirkos's only son, Nikola, age twelve. Nikola was the nephew and heir of the childless reigning prince of Montenegro Danilo I. In 1856, after the death of her mother, Milena was sent to Cetinje, to be raised in the household of her future in laws. Having grown up according to the rudimentary customs of Montenegro at that time even in prominent families, Milena was illiterate. Between 1856 and 1860 she grew up in the household of Mirko Njegoš, her soon to be father in law, raised alongside Mirko's daughter, Anastasia. During those four years she became close to her new family: "My father and mother loved her as their own daughter" wrote later King Nikola. "My late uncle, also loved her greatly and treated her as his own child, and she showed him her love and respect in every way. She was very beautiful, sweet, kind, gentle and devout." In those years Milena seldom saw her future husband. Six years her senior, Nikola meanwhile was educated first in Trieste and later in Paris.
The assassination of Prince Danilo, on 12 August 1860, unexpectedly made Nikola the reigning prince of Montenegro at age eighteen. Shortly after, Nikola was close to death ill with pneumonia. When he recovered, it was decided to arrange his marriage as soon as possible in order to provide Montenegro with an heir. Milena's father traveled to St Petersburg and informed Tsar Alexander II of Russia, Montenegro's greatest ally and supporter, of the marriage. On 8 November 1862, at the age of 14, Milena married Prince Nicholas I of Montenegro, then aged 21, who later became King in 1910. The wedding was a simple affair and was held in the Vlach Church in Lovćen valley. The marriage was political: her family had played an important role in Montenegin politics and was befriended with the House of Petrović-Njegoš, her husband's family. Only in her early teens at the time of her marriage, Milena's early years as Princess consort were difficult. She was inexperienced and was a solitary figure initially overshadowed by Princess Darinka, widow of Prince Danilo, who was close to Nikola. During the first four years of her marriage, she did not have any children. She was tutored in the Serbian language and learned French. Milena asserted her position after Darinka left Montenegro for good. In 1865, Milena gave birth to the first of her twelve children. Between 1865 and 1869, she had four daughters in quick succession, with a son and heir, Prince Danilo, born in 1871, and seven more children would follow. Milena's relationship with her husband solidified with time and she became respected and influential. While her husband was away in visits to Austria-Hungary and Russia in the winter of 1868–1869, Milena was in charge of court affairs. She had visited İstanbul with her husband after the invitation of Sultan Abdulhamid in 1899. She was one of the foreigners who had the opportunity to enter the Sultan's harem. After the annexation by the Kingdom of Serbia in 1918, the royal family was forced into exile. Milena died in France, two years after her husband and was buried in San Remo, Italy. In 1989 her remains, together with her husband's and Xenia's and Vera's, two of her daughters, were transferred to Cetinje and reburied in the Cipur-chapel.
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The couple had twelve children: three sons and nine daughters, some of whom married European royalty.
