Maria Anna of the Palatinate-Neuburg was born on 28 October 1667, in Benrath Palace, Düsseldorf, Germany. She was the daughter of Elisabeth Amalie of Hesse-Darmstadt (20 March 1635 - 4 August 1709) and Philip Wilhelm of Neuburg, Elector Palatine (24 November 1615 - 2 September 1690). Her maternal grandparents were Sophia Eleonore of Saxony and George II, Landgrave of Hesse-Darmstadt. Her paternal grandparents were Magdalene of Bavaria and Wolfgang Wilhelm, Count Palatine of Neuburg. Maria Anna's parents were married on 3 September 1653. Her siblings were: Eleonor Magdalene (1655-1720), Maria Adelheid (1656-1656), Sophia Elisabeth (1657-1658), Johann Wilhelm (1658-1716), Wolfgang George (1659-1683), Ludwig Anton (1660-1694), Karl Philip (1661-1742), Alexander Sigismund (1663-1737), Franz Ludwig (1664-1732), Frederik Wilhelm (1665-1689), Maria Sophia (1666-1699), Philip Wilhelm (1668-1693), Dorothea Sophie (1670-1748), Hedwig Elisabeth (1673-1722), Johan (1675-1675) and Leopoldine Eleonora (1679-1693). Her sister, Eleonor Magdalene of the Palatinate-Neuburg married Leopold I, Holy Roman Emperor (1640-1705) in 1676. Maria Anna of the Palatinate-Neuburg married Carlos II, King of Spain (6 November 1661 - 1 November 1700) by proxy on 28 August 1689, in Ingolstadt, Germany. He was the son of Mariana of Austria (24 December 1634 - 16 May 1696) and Felipe IV, King of Spain and Portugal (8 April 1605 - 17 September 1665). Maria Anna was his second wife. Carlos II married first, Marie Louise d'Orléans (26 March 1662 - 12 February 1689) on 19 November 1679, in Quintanapalla, Spain. Marie Louise died on 12 February 1689, in Madrid, Spain. They had no children. Maria Anna and Carlos II were married in person on 14 May 1690, in San Diego, near Valladolid. Her sister, Dorothea Sophie of the Palatinate-Neuburg married Odoardo II Farnese on 17 May 1690. Her father, Philip Wilhelm of Neuburg died on 2 September 1690. Maria Anna and Carlos II had no children. Her mother, Elisabeth Amalie died on 4 August 1709. Her sister, Eleonor Magdalene died on 19 January 1720, in Wien, Austria. Carlos II died on 1 November 1700, at Royal Alcazar, in Madrid, Spain. He was interred in the El Escorial, Spain. He was succeeded by Philip V. Maria Anna of the Palatinate-Neuburg died aged 72, on 16 July 1740, at Infantado Palace, in Guadalajara, Spain. She was interred in the El Escorial, Spain.