Henriette Maria war das neunte Kind des Kurfürsten Friedrich V. von der Pfalz und Königs von Böhmen und seiner Gattin Elisabeth Stuart und die einzige Tochter mit blonden Haaren. Von ihrer Mutter wurde sie "Nennie" genannt. "Princess Henrietta, who had inherited her mother's cloud of fair curly hair and large grey-blue eyes, was distressingly fragile. More than once her family thought that they had lost her. She was universally beloved, for she was as sweet-tempered as her appearance promised." (in: Carola Oman: Elizabeth of Bohemia, id., p. 384).
Ihre jüngste Schwester Sophie von der Pfalz berichtet über sie: "My sister Henriette bore no resemblance to the other two [ihren Schwestern Elisabeth und Louise Hollandine]. She had fair flaxen hair, a complexion, without exaggeration, of lilies and roses, and a nose which, although well shaped, was able to resist the cold. She had soft eyes, black well-arched eyebrows, an admirable contour of face and forehead, a pretty mouth, and hands and arms as perfect as if they had been turned with a lathe. Of her feet and ankles I need say no more than that they resembled those of the rest of her family. Her talents, by which I chiefly profited, lay in the direction of needlework and preserve-making." (in: Memoirs of Sophia, Electress of Hanover: 1630-1680, id., pp. 15-16).
Am 16. Mai 1651 wurde sie mit dem Fürsten Sigmund Rákoczy von Siebenbürgen verheiratet. Sie starb bereits vier Monate später. "She died suddenly and peacefully on a September morning." (in: Carola Oman: Elizabeth of Bohemia, id., p. 388). Sie schien in ihren Gatten sehr verliebt gewesen zu sein. An ihre älteste Schwester Elisabeth schrieb sie Folgendes: "Prince Siegmund was 'very stately'. He drove always with six horses. If he had a single fault it was that he was too kind, too generous. A little sister could not thank the Elector Palatine enough for her happy marriage. All the new relations were caressing her. Yesterday she had put on for the first time the national costume of her new country. 'I looked so pretty in it that my lord's mother could not express her pleasure, yet it is not at all a splendid dress - quite bürgerlich, resembling that worn by the peasants.'" (in: Carola Oman: Elizabeth of Bohemia, id., p. 387).