Marilène van den Broek obtained her highschool diploma (pre-university secondary education) in Wassenaar in 1988.

She studied from 1988 to 1994 at the University of Groningen where she received her MSc degree in Business Administration.

Princess Marilène currently works at the Rijksmuseum Amsterdam, a Dutch national museum dedicated to arts, crafts, and history.

She married Prince Maurits of Orange-Nassau, van Vollenhoven in Apeldoorn civilly on 29 May 1998, followed by a religious ceremony on 30 May.

His Highness Prince Maurits is the eldest son of Princess Margriet of the Netherlands and Pieter van Vollenhoven.